JPH03199334A - Titanium material having good chasing property and application goods thereof - Google Patents

Abstract

PURPOSE:To provide the Ti material as an ornaments member having the good chasing property to allow, for example, rapid and easy working by specifying an oxygen content to a specific value or blow to increase the purity of the material. CONSTITUTION:The above mentioned Ti material has <=600ppm oxygen content and further preferably <=100ppm and consists of the balance Ti and incidental impurities. The incidental impurities include nitrogen, carbon, Fe, Ni, Cr, Al, K, Na, etc., and may be incorporated into the material to the extent of not disturbing the function of the desired object. The oxygen improves the chasing property ('ease of carving') with a decrease in the content thereof in the Ti material and the upper limit thereof is 600ppm. The carving of characters and ornamental patterns is extremely easy according to the Ti material having such chasing property. The excellent member for ornamentation having the ornamental characteristic in combination is obtd. from a chemically treated layer having wear resistance.

Description

[Detailed description of the invention] [Object of the invention l (Industrial application field) The present invention relates to a titanium material with good engraving properties.

(Prior Art) Decorative parts are typified by metals and plastics, and are used in various arts and crafts such as clothing accessories, watches, and eyeglass parts.

Under these circumstances, metal decorative parts such as titanium have recently been attracting attention because of their smart designs and excellent functionality. The functions referred to here are abrasion resistance and "ease of carving" into metal, and this "ease of carving" is referred to as "metal engraving" in the present invention. As mentioned above, decorative materials have a wide variety of uses, but here we will focus on seals made from titanium, which has good engraving properties.

Typical examples include eyeglass parts and brooches.

Traditionally, ivory has been the mainstream as a high-quality stamp material,
Recently, Japan's import of ivory has attracted international criticism, leading to poaching and overhunting of elephants.

There is a demand for printing materials with excellent fineness and abrasion resistance. That is, a seal requires abrasion resistance because the stamp surface contacts the paper, and decorativeness is also an important element because it symbolizes an individual. From these points of view, ivory is the preferred material for stamps.

In addition to traditional materials such as buffalo horn and 9 stones, metals such as titanium, gold, and silver have recently attracted attention. Titanium in particular can be said to be an excellent stamping material because it has very little wear and there is no need to worry about corrosion or deformation.

However, titanium is expensive and extremely hard, which means it does not have excellent engraving properties, and requires special engraving techniques such as using a special machine, leading to problems such as long production times and a failure to satisfy the craftsmanship. .

Furthermore, the inventors of the present invention have investigated that when the surname "Yamanobe" shown in Figure 1 is engraved on a conventional seal using titanium as a stamp material, when paying attention to the character "No", it is found that It is said that the four holes in the part ``Ten'' are easily connected because the ``10'' cannot be carved properly, and it takes an extremely long time to carve a part that requires such precise techniques, resulting in extremely low work efficiency. We found a problem, that is, a lack of metal engraving, which is a particularly subtle part of workability.

Next, as shown in Figure 2, the eyeglasses that we focused on as another example of ornaments have temples 1. Eye rim 2゜yama 3. Box 4. Foot 5. Rim lock 6, hinge 7, crossing 8. Decoration 9. It is formed by combining various parts such as the screw 10. Among the materials used for these eyeglass parts, metals have recently been attracting attention due to their superior functionality and novel designs. Conventionally, the metal materials that make up the parts of these metallic eyeglasses include nickel-chromium alloy, stainless steel, nickel silver, and phosphor bronze, and each material is used differently for each eyeglass part by taking advantage of its characteristics. There is. These materials are required to have good spring properties and corrosion resistance, high strength, and excellent gloss and polishability. For example, temples, eye rims, legs, crests, and legs must have excellent spring characteristics because they affect stability when worn, and temples that often come into contact with the human body must be corrosion resistant. It is said that

In other words, many parts of eyeglasses come into direct contact with human skin during handling, and there are also parts that are touched by hands, and each part requires some of the above-mentioned characteristics from the viewpoint of assembly and decoration. , metal materials that are compatible with this are used. Therefore, titanium is attracting attention from the viewpoint of wear resistance and decoration, but it is also expensive and
In addition, it has poor engraving properties, making it difficult to make small holes in the pins 4 and hinges 10, and to form complex structures, and it is difficult to carve fine patterns.

Brooches also have the functions needed to decorate accessories.
That is, there is a demand for materials that can be molded into complex structures, carved with fine patterns, and exhibit beautiful color tones. However, although titanium is excellent in terms of wear resistance and decoration, it is too hard to be crafted into jewelry.
In other words, there was a problem in that the carving quality was poor.

(Problems to be Solved by the Invention) As described above, conventional titanium has extremely poor engraving properties, making it difficult to precisely work it into various ornamental parts. The object of the present invention is to eliminate the above-mentioned drawbacks and provide a titanium material as a decorative member having good engraving properties that can be easily worked in a short time. By providing a hard layer on the surface, it is possible to improve abrasion resistance and decorative properties.

] Structure of the invention l (Means and effects for solving the problem) The present inventors,
As a result of extensive experimental studies on the wear resistance and decorative properties of titanium, we found that the gas components in titanium, especially the oxygen content, were
It has been found that when the content is reduced to 0 ppm or less and the purity is increased, the delicate engraving properties required for seals, etc., that is, the "easiness of engraving", significantly increases.

That is, in the first invention, the oxygen content is substantially 600 pp.
It is a titanium material with good engraving properties, characterized by containing less than m and other incidental impurities. Incidental impurities include nitrogen, carbon, iron, and nickel.

These include chromium, aluminum, potassium, and sodium. These impurities impair processability and corrosion resistance, so it is better to have fewer impurities, but they may be included as long as they do not interfere with the functions of the target product.

Oxygen is an element that, when reduced in content in titanium materials, improves its engraving properties, ie makes it significantly easier to form complex structures and carve fine patterns. Therefore, specifically, the present invention requires that the content be 6001111!1 or less.

Desirably 250 ppm or less, more preferably 100 ppm or less
ppa+ or less is better. Additionally, it is an element that also has the effect of improving the abrasion resistance and color decoration of the titanium surface.

Nitrogen, like oxygen, has the effect of improving the engraving properties of titanium materials as its content decreases, and is also an effective element for improving the wear resistance and decorative properties of the titanium surface. Therefore, the content is 50 ppm or less,
More preferably, the content is 20 ppm or less. Note that the nitrogen content inevitably decreases as the oxygen content decreases.

The second invention is that the hardness of the titanium material of the first invention is such that it can be easily and precisely worked in a short time without using special means. In other words, if we first consider seals as decorative items, as shown in Figure 1, when carving the characters ``Yamanobe,'' detailed techniques are required, such as the part of ``Satohen'' in ``No'' and ``Sato''.
In order to carve the four holes of the ``field'' and the curved lines of the ``sides'', it is necessary that the engraving properties of the stamp material be good to some extent. However, because the oxygen content of conventional titanium has not been sufficiently reduced, even skilled workers cannot perform these tasks easily.
The present invention has made it possible for the first time to achieve the excellent engraving properties required for ornamental parts. Also, in the eyeglass parts shown in FIG. 2, the temple 1° and the eye rim 2. Yama 3. In order to form a special shape using a press or carve a rough pattern into one piece, the material needs to have a certain degree of engraving ability, and in addition, it also needs to have decorative properties such as a glossy color. Furthermore, a pair of glasses contains dozens of fine holes to connect individual eyeglass parts, and in order to increase production efficiency for mass-produced products, these fine and precise holes must be drilled in the titanium material in a short time. Machinability is required. Specifically, conventionally it took 2 seconds to drill a single hole, but by improving machinability using the present invention, the time to drill a hole has been shortened to 1 second. Therefore, since the entire pair of eyeglasses has several dozen holes, the production efficiency is significantly increased to several tens of values when converted to a pair of eyeglasses, making it possible to reduce costs.

The present inventors have discovered a titanium material with excellent engraving properties that combines these properties and is an unprecedented ornamental member. Similarly, accessories such as brooches as shown in Figure 3 can be molded into complex structures such as the contours and undulations of the face.
The "titanium of the present invention" is required to have the ability to engrave each hair strand and also exhibit a color suitable for decorative parts.
is extremely effective.

In the third and fourth inventions, a hard layer with a Vickers hardness of 500 or more is provided on a part of the surface of the titanium material. After molding or inscribing a pattern, the surface of the ornamental member needs to have wear resistance in order to increase the durability of the accessory. In particular, seals require abrasion resistance because the stamp surface with engraved characters comes into direct contact with the paper. As a result of studying this wear resistance, the present inventors found that by chemically treating the surface of titanium material and providing an oxidized or nitrided layer, the wear resistance increases and it becomes both decorative and durable at the same time. I found out. Although the oxide layer and nitride layer on pure titanium have some difference in hardness, both have sufficient hardness to maintain their wear resistance. The thickness of the layer is preferably 0.5 to 5 microns. If the layer is too thin, the wear resistance effect will not be as expected;
On the other hand, if it is too thick, the layer will easily peel off. The thickness of the layer also affects the color; for example, in the case of an oxidized layer, the color changes subtly from purple to blue depending on the thickness of the layer. The thickness of this layer depends on the oxygen concentration, treatment time and treatment temperature.

The eighth invention is that the surface layer of the titanium material has a recrystallized pattern. That is, the present inventors have also discovered that when the above-mentioned oxide layer and nitride layer are heat-treated at a temperature higher than the recrystallization temperature in an oxygen or nitrogen atmosphere, a scale-like or linear recrystallization pattern as shown in FIG. 4 is produced on the surface of the stamp material. found out. This property indicates that the pure titanium of the present invention is very useful as a decorative article member.

As described above, the high-purity titanium of the present invention, which has an oxygen content of 600 ppm or less and has good carving properties, is as easy to engrave as, or superior to, precious metals such as ivory, gold, and silver. oxidation layer.

The wear resistance of the surface layer, such as the nitrided layer, is also comparable to conventionally used materials. In addition, these layers have unique colors such as purple and golden yellow, and they also have the decorative property of creating a crystalline pattern, so they can be used for things such as seals and glasses that require wear resistance and decoration. It is extremely effective as a material for jewelry. In addition, the pure titanium can be modified in various ways without departing from the gist of the present invention.

The Ti material of the present invention can be manufactured, for example, as follows.

First, acicular Tf is manufactured by molten salt electrolysis. For example, sponge Ti is used as the Ti raw material. The electrolytic bath is preferably KC1-NaC1, and the electrolytic temperature is 730 to 755°C.

Voltage 6.0-8. Ov is preferred.

By performing molten salt electrolysis under such conditions, oxygen is usually 70 to 160 ppm; Fe, Cr, and Nj are each 0. 75-6ppm; Na and K are each 96
Acicular Ti with ~325 ppo+ is obtained.

The obtained acicular Ti is then fed into an EB melting furnace while preventing contamination from the outside. The acicular Ti obtained by the above molten salt electrolysis method is usually compacted by pressing,
It is conceivable to melt this using EB as an electrode, but in that case, it will be contaminated by contact with tools and deformation during compact molding, so in the present invention, in order to prevent this external contamination, acicular Ti It is preferable to directly introduce the granules into vibrator-type granules in a vacuum and then perform EB melting.

In the EB melting furnace, the inside of the furnace is 5 x 10-'mbc
The E of the needle-shaped Tl is
B Perform lysis.

Although the operating conditions for dissolving EB are not particularly limited, it is required to select the dissolution rate in consideration of absorption of contaminants such as oxygen. For example, 1°75~2. 3Kg
/br is the preferred condition.

The oxygen content in the EB cast material obtained through this process is 6
00 ppm+ or less, preferably 250 ppm or less,
More preferably, it is suppressed to 100 ppm or less.

For example, the Ti material of the present invention is manufactured by the method described above.

(Example) Next, the present invention will be specifically explained using examples.

The high purity titanium of the present invention shown in Table 1 was obtained by the following manufacturing method.

"Example 1" A titanium sponge was placed in a reaction vessel, iodine gas was fed thereto to generate TiI4, and then only Ti was precipitated and purified on a filament at 1200°C to produce crystalline Ti. Then 5.
In a vacuum of 0XIV'' Torr, this crystalline Ti was suspended as a consumable electrode and melted with an electron beam, and was water-cooled in a copper mold to produce an ingot.

This ingot was cold-forged, cold-rolled, and then annealed at about 700° C. below the recrystallization temperature to obtain a titanium material.

"Example 2" An electrolytic bath was filled with chloride-based KCl-N5C1, etc., and a titanium sponge was heated at 730 to 755°C with a temperature of 6.0°C.
~8. It was electrolytically purified using Ov. Next, this sponge titanium was suspended as a consumable electrode in a vacuum of 5,000 ml-II Torr and melted with an electron beam, and was water-cooled in a copper mold to produce an ingot. This ingot was cold-forged, cold-rolled, and A titanium material was obtained by annealing at about 700° C. below the recrystallization temperature.

"Example 3" An electrolytic bath was filled with chloride-based KCl-NlCl, etc. as an electrolytic bath, and a titanium sponge was heated at 730 to 755°C with a temperature of 6.0°C.
Electrorefined at ~8.0V. Next, this titanium sponge was suspended as a consumable electrode in a vacuum of 1,0XIO-'To+r, melted with an electron beam, and water-cooled in a copper mold to produce an ingot. This ingot was cold-forged, cold-rolled, and then annealed at about 750° C. below the recrystallization temperature to obtain a titanium material.

"Example 4" An electrolytic bath was filled with chloride-based KCl-NiCl, etc. as an electrolytic bath, and sponge titanium was heated at 73° C. (1 to 755° C., 6.5° C.).
0-/I1. It was electrolytically purified using OV. Next, this sponge titanium was used as a consumable electrode and melted and refined in an arc furnace to produce an ingot. This ingot was cold-forged, cold-rolled, and then annealed at about 8 DO°C below the recrystallization temperature to obtain a titanium material.

"Comparative Example 1" A commercially available titanium sponge with a low oxygen content was pressed, used as an electrode, melted and purified in a 5.0 x 10-'T high vacuum arc furnace, and then water-cooled in a copper mold to obtain an ingot.

"Comparative Example 2" A commercially available titanium sponge was pressed and used as an electrode.3.
After arc melting in A of 0XIO-'Tot+, it was water-cooled in a copper mold to obtain an ingot.

The engraving properties of seals, eyeglass parts, and brooches were investigated using the high-purity titanium shown in Table 1.

First, the seals were engraved by hand. The characters are printed using the markings shown in Figure 1.Here, we focused on the part of ``田'', which requires special engraving ability, and engraved 40 times in 8 hours, to see how many times we succeeded. was measured. Success here means that there are no missing parts and it can be handled as a commercial product. As a result, as shown in Table 1, the stamp material using the pure titanium of the present invention, which had a lower oxygen content than the conventional stamp material, had extremely excellent engraving properties.

Eyeglasses are made up of various parts as shown in Figure 2, but as mentioned above, the individual parts are connected through minute holes, and here we will focus on how easy it is to make these holes. Holes were drilled in the titanium material of each example using a small drill, and the number of holes that could be drilled in one minute was compared and examined. As a result, as shown in Table 1, when the high purity titanium of the present invention was used, the number of holes that could be made in a unit time was extremely large due to its excellent machinability.

For brooches, we compared the engraving performance by carving objects that require skill, such as the ``cameo'' shown in Figure 3, such as facial contours and complex expressions. The evaluation here was performed as follows.

A: The outline of the face, complex expressions, and the flow of hair can be seen B: The outline of the face and the flow of hair can be seen, but the facial expressions are unclear C: Eyes, nose , I can see that the face and mouth are covered in hail.

D... I don't know what you are trying to express.

As is clear from Table 1, the brooches of the examples of the present invention have extremely good engraving properties compared to the comparative examples.

Next, a layer having a recrystallized pattern was formed in each of Examples 1 to 4 by the following procedure.

The high purity titanium obtained in the above example was heat treated in a nitrogen atmosphere or an oxygen atmosphere at a temperature above the recrystallization temperature for 3 hours to provide a nitride layer or an oxide layer having a recrystallization pattern on the surface of the high purity titanium of the present invention. .

In order to improve the wear resistance of this layer, 1) After inscribing characters or decorative patterns, the entire layer is nitrided or oxidized. 2) Prevent nitriding or oxidation by applying nitriding borax to the surface on which letters or decorative patterns are to be engraved, first apply a layer to other surfaces, then etch the letters or decorative patterns, and then nitride only that surface. Alternatively, a method of oxidation was used. Furthermore, since these layers exhibit a purple or golden color, they are ideal for decorative members including recrystallized patterns.

As an example, a seal was manufactured using the decorative member obtained by the above method, and an abrasion resistance test was conducted. Press on copy paper 3
The degree of abrasion of the stamp surface was measured by repeatedly stamping with a load of kg and removing the paper while pressing. As a result, as shown in Table 2, the high purity titanium of the present invention had less wear than ivory.

As described above, the high-purity titanium of the present invention is a decorative member that is comparable in engraving and decorative properties to noble metals such as ivory, gold, and silver, and has excellent wear resistance.

The following margins [Advantageous Effects of the Invention 1 As detailed above, the ethane material with good engraving properties of the present invention makes it extremely easy to engrave characters and decorative patterns, and it also has abrasion-resistant abrasive treatment. An excellent decorative member is obtained in which the layer has decorative properties, and its usefulness is tremendous.

[Brief explanation of drawings]

Figure 1 is a conventional stamp of characters engraved on pure titanium, Figure 2 is a perspective view of glasses, Figure 3 is a brooch with a human face engraved on high-abundance titanium according to the present invention, and Figure 41 is a brooch with a human face engraved on the surface of the titanium material. This is the resulting recrystallization pattern. 1... Temple 3... Mountain 5... Foot 7... Hinge 9... Ornament 11... Recrystallization pattern

Claims (10)

[Claims] (1) A titanium material with good engraving properties, characterized by an oxygen content of 600 ppm or less, and the remainder being substantially titanium. (2) A titanium material with good engraving properties according to claim 1, characterized in that the titanium material has a hard layer provided on at least a part of its surface. (3) The titanium material with good engraving properties according to claim 2, wherein the hard layer on the surface of the titanium material has a Vickers hardness of 500 or more. (4) The titanium material with good engraving properties according to claim 2, characterized in that the thickness of the layer is 0.5 to 5 μm. (5) The titanium material with good engraving properties as set forth in claim 2, wherein the hard layer is a nitride layer. (6) The titanium material with good engraving properties as set forth in claim 2, wherein the hard layer is an oxide layer. (7) The titanium material with good engraving properties according to claim 2, which has a recrystallized pattern on at least a portion of the layer surface. (8) A seal characterized in that the oxygen content is 600 ppm or less, and the remainder is substantially made of titanium. (9) A glasses component characterized in that the oxygen content is 600 ppm or less, and the remainder is substantially made of titanium. (10) An accessory characterized in that the oxygen content is less than 600 ppm, and the remainder is substantially made of titanium.