Construction material from pure titanium and method for manufacturing the same

FIELD: metallurgy, in particular, titanium-based materials resistant to change of color.

SUBSTANCE: construction material of pure titanium contains, wt%: Fe 0.08 or less; Nb 0.02 or less; Co 0.02 or less, and is provided with surface oxide film having thickness of 170Å or less. Method involves producing material from pure titanium; etching and heating to temperature X( C) within the range of from 130 C to 280 C for time T (min) satisfying condition of T≥239408xX-2,3237.

EFFECT: increased resistance to change of color for prolonged time as compared to traditional materials.

3 cl, 2 dwg, 4 tbl, 3 ex

 

PREREQUISITES TO the CREATION of INVENTIONS

The scope of the invention

The present invention relates to a building material made of pure titanium, which is resistant to color change over a long period of time, for the construction of external walls of buildings and reinforcing elements and to a method of manufacturing such a material made of pure titanium.

Description of the prior art,

Material titanium has a surface covered with an oxide film, which has excellent resistance to corrosion, has excellent corrosion resistance and mechanical properties. Building materials made of titanium are of particular interest due to their excellent properties.

Modern development of port areas and modern gradually deteriorating environmental conditions around buildings due to acid rain create a variety of problems. Today's tough environmental conditions, which are the building materials of titanium, cause a change in color of building materials of titanium from silvery-white to brownish with age. Changed its color materials of titanium does not have glitter inherent in a beautiful metallic colors and damage the aesthetic design of buildings. Although there are opportunities to update the initial view materials from t the Tana, changed its color during aging, by repair work, including smoothing or polishing, such repairs are very expensive, and for some parts of buildings such repairs are excluded. Accordingly, studies have been conducted on the development of materials from titanium, which is resistant to color change for a long time.

Material titanium, or material of titanium alloy described in JP-A-10-8234 has a surface that is completely finished to surface roughness of Ra=3 μm or less and is covered with an oxide film thickness of 20 Å or more to contain the color change for a long time. Materials titanium and titanium alloy described in Japanese patent No. 3255610 have an oxide film with a thickness of 100 Å or less and the surface layer having a certain content of C.

A technology designed to solve the problems arising from changes color over a long period of time by providing specific content in the surface layer described in JP-A-2001-348634. In the process of manufacturing sheet of titanium in accordance with this technology produce annealing of cold-rolled sheet of titanium at a temperature of from 750 to 800°C for 3-5 minutes to remove the layer having a high content of C, which is considered a cause of color change during a long time.

Requirements for containment color change for a long time of construction materials from titanium gradually become tougher in recent years, and in this regard there is an urgent need to develop materials of titanium, more resistant to color change over a long period of time. Test data referred to in the preceding three reference documents are qualitative, not quantitative. Materials of titanium should be assessed using a more precise evaluation systems for development of materials from titanium that meet stringent requirements.

Although a variety of building materials made of pure titanium, which is resistant to color change for a long time, already present in the market, required building materials made of pure titanium, which has further improved resistance to color change over a long period of time, because the rigidity of the structure of buildings is gradually increased, and the cost of repairs increases progressively in recent years.

SUMMARY of the INVENTION

Accordingly, the aim of the present invention is to provide a material of pure titanium having a bógreater resistance to color change over a longer period of time than traditional materials of titanium.

Were studied various Mat the materials of titanium, in order to solve the above problems, and implemented a strict assessment of the resistance to color change over a long period of time materials of titanium. In the result it was found that certain impurities contained in the materials of titanium, have influence on the resistance to color change over a long period of time materials from titanium.

Pure titanium and titanium alloys used for the manufacture of construction materials from pure titanium. Building materials from the most pure titanium are made of industrial pure titanium Grade 1 JIS (Japanese industrial standards), containing small amounts of impurities and having superior formability. Even if building materials made of titanium made of material not containing scrap titanium and containing only industrial titanium Grade 1 JIS, i.e. sponge titanium, construction materials titanium inevitably contain various impurities in small amounts. Chemical requirements for industrial titanium Grade 1 JIS determine the content of impurities, including oxygen and iron content, in terms of formemost. The content of such impurities while improving resistance to color change for a long time did not paid attention.

The authors of the present invention found that the net building the mother of the crystals, made from pure titanium, with certain impurity content is below the predetermined value, almost no change in color for a long time and have established the present invention.

In accordance with the present invention is a construction material made of pure titanium are made of pure titanium having a Fe content of 0.08 wt.% or below, the Nb content of 0.02 wt.% or less and a content of 0.02 wt.% or less.

Preferably, the construction material of pure titanium has a surface oxide film thickness 170 Å or less. Although the building material of pure titanium having a thicker surface oxide film has a lower resistance to color change over a long period of time, the building material of pure titanium has a beautiful silver-white color, and the growth of the surface oxide film can be effectively restrained, when the building material of pure titanium has a composition defined, as described above, and the thickness of the surface oxide film is 170 Å or less. Therefore, the construction material of pure titanium having a surface oxide film thickness 170 Å or less not reported a change of colour for a long time before this magnitude, which spoils the aesthetic design, and retains took silver at the IMS-white appearance.

A method of manufacturing a building material made of pure titanium in accordance with the present invention involves the following stages: preparation of building material of pure titanium having a Fe content of 0.08 wt.% or below, the Nb content of 0.02 wt.% or less and a content of 0.02 wt.% or below, the etch construction material of pure titanium; and heat treatment must be performed construction material of pure titanium at a temperature X (° (C) in the range from 130 to 280°during the heating time T (min) in order to satisfy the condition expressed as: T≥239408×X-2,3237.

At the stage of heating the formed surface oxide film of the proper thickness, effective in curbing harmful staining, and reduced content of impurities, which also causes the color change. Thus, a construction material made of pure titanium, produced by the method of manufacturing a building material made of pure titanium, has a high resistance to color change for a long time.

Having a very high resistance to color change for a long time, much higher than traditional building materials from titanium or titanium alloy, a building material made of pure titanium according to the present invention is very useful as a building material is in the construction of buildings, for which requirements to aesthetic design are essential, which are exposed to sea wind and acid rain, which require expensive maintenance repair and are difficult to repair. Thus, the construction material of pure titanium according to the present invention is very useful from the point of view of its industrial use.

BRIEF DESCRIPTION of DRAWINGS

The above and other objectives, features and advantages of the present invention will be more apparent from the following description, which considered in connection with the attached drawings, on which:

Figure 1 is a graph illustrating the ECO method for measuring the thickness of the oxide film; and

Figure 2 is a graph showing the relationship between heating time and temperature of heating is effective in enhancing the resistance to color change for a long time.

Description of the PREFERRED OPTIONS of the INCARNATION

The most distinctive feature of the construction material of pure titanium in accordance with the present invention is that the color change for a long time a building material made of pure titanium is very slow, even when the construction material of pure titanium is used for Stroitel the CTV building, exposed to harsh environmental conditions.

Although building materials from titanium or titanium alloy, which is resistant to color change over a long period of time, available for sale on the market, their resistance to color change over a long period of time is insufficient. Even traditional corrosion-resistant construction materials of pure titanium will change colour over time. It was found that certain impurities contained in the building material of pure titanium, affect the color change of the construction material of pure titanium for a long time and that the construction material of pure titanium containing controlled amounts of impurities, has a high resistance to color change over a long period of time even under severe environmental conditions, which led to the creation of the present invention.

Construction material of pure titanium in a preferred variant embodiment in accordance with the present invention is prepared from pure titanium having a Fe content of 0.08 wt.% or below, the Nb content of 0.02 wt.% or less and a content of 0.02 wt.% or below. Fe, Nb, and Co contained in the pure titanium that is part of a building material made of pure titanium, cause a change in color for a long time Stroitel the aqueous material of pure titanium. This fact was discovered by the authors of the invention. The sign of color changes for a long time a building material made of pure titanium can be significantly slowed down by controlling the values of Fe, Nb and Co in pure titanium below the previously defined values of Fe, Nb and SB. When determining the impurity content of the expression "X wt.% or lower" means that pure titanium does not contain impurities or contains impurities in a negligibly small quantity. The content expressed in "percent by mass", which can be represented hereinafter as a "percentage". Preferably, the Fe content is 0.06% or less (more preferably 0.05% or below) the content of Nb is of 0.015% or less (more preferably 0.01% or below) and the Co content is of 0.015% or less (more preferably 0.01% or below).

To obtain pure titanium having a content of Fe, Nb and Co, not to exceed the previously defined values of Fe, Nb and Co, the content of Fe, Nb and Co in the material of the raw titanium installed. More specifically, the content of impurities in the spongy titanium, i.e. from raw material titanium, are measured, and the titanium sponge is used, if it has a value of Fe, Nb and Co, not more than a certain previously, the contents of Fe, Nb and SB.

The term "pure titanium", used C the ect, means a substance containing Fe, Nb and in quantities not exceeding certain values of Fe, Nb and Co, and inevitable impurities, and Ti as the remainder.

Preferably, the thickness of the surface oxide films prepared building material of pure titanium is 170 Å or less. Construction material of pure titanium having a surface oxide film thickness 170 Å or less and has a composition defined by the present invention, has a beautiful silver-white color, characterizing the Titan. Construction material of pure titanium according to the present invention effectively inhibits the growth of surface oxide film, which causes the color change and, consequently, the construction material of pure titanium is excellent as a building material.

The thickness of the surface oxide film can be adjusted by adjusting the growth conditions of the surface oxide film during the manufacture of the construction material of pure titanium. The surface oxide film grows as a building material made of pure titanium is exposed to oxygen contained in the atmosphere, in the continuation of the annealing process, and is removed through etching. Therefore, the thickness of the surface oxide film can be cut at gulirovanie by regulating the vacuum during vacuum annealing, workpiece temperature at the beginning of the exposure atmosphere subjected to vacuum annealing item, or the degree of rinsing after pickling process. More specifically, the thickness of the surface oxide film of the sample and the conditions for the formation of a surface oxide film re-regulated to determine the desired conditions.

Although there are no specific limitations to the method for measuring the thickness of the surface oxide film, the thickness can be measured, for example, by means of auger electron spectroscopy. As shown in figure 1, the thickness of the surface oxide film can be determined by multiplying the time of spraying required to reduce the oxygen concentration to the average oxygen concentration between the maximum oxygen concentration and the main oxygen concentration on the deposition rate, i.e. (the Thickness of the surface oxide film) = (Time of deposition t) × (deposition Rate). The deposition rate can be determined by the speed of deposition, in which a film of SiO2is deposited by sputtering, in accordance with the measurement conditions of deposition.

In General, the method of manufacturing a building material made of pure titanium according to the present invention includes at least a process of manufacturing an ingot, hot rolling process, the Ho process is one of rolling and the final finishing process. The conditions for these processes can be the same as for the well-known processes. The final finishing process, following the cold rolling process must be carefully planned, because the process of finishing has a significant influence on the properties of the material surface of Titan.

For example, the process final finish final finish material titanium is a process of vacuum annealing (IN process) or a process of atmospheric annealing and etching (AOT process final finish). It is clear that the surface oxide film of material of titanium, completely finished by the process contains a large amount of C, which causes a color change in a long time. Therefore, when finishing material of titanium is preferably used etching process. A method of manufacturing a building material made of pure titanium may include additional process, provided that the additional process will not spoil the effect of etching. For example, the workpiece processed by etching, can be completely finished light roll pass through the surface layer) using matting rollers on the matte surface, in order to improve the design (clarity) of the workpiece.

When p is the surface of the workpiece processed by etching in the process of finishing, material of titanium having a high resistance to color change over a long period of time, can be obtained by thermal treatment process etched workpiece, in which potraviny the workpiece is heated at a temperature of X (° (C) in the range from 130 to 280°during the heating time T (min) in order to satisfy the condition expressed as T≥239408×X-2,3237. Heating the workpiece at temperatures in the range from 130 to 280°does not cause harmful changes in color, which spoils the design, and the heat treatment process, satisfying the condition represented by this expression, additionally improves the resistance to color change over a long period of time. Although the reason why the heat treatment process improves the resistance to color change over a long period of time, are not known precisely, it is assumed that the process of heat treatment changes the structure of the oxide film.

Sometimes harmful color change occurs when the workpiece is heated to a high temperature not lower than 250°With (from 250 to 280° (C) for a long time in the atmosphere. Thus, it is required to heat the workpiece for a period of not more than 30 min, preferably 10 min or less, when processing the " item must be heated to such high temperatures. Even if there is a color change, the workpiece is painted at the initial stages of color change in a very light Golden colour that improves the design, instead of spoiling it. In some cases, heating may be stopped at this initial stage, to ensure that the color change of the construction material of pure titanium in a very light Golden color.

During thermal processing of the workpiece is heated or in a vacuum atmosphere or in an atmosphere environment. Any upper limit on the time of heating is determined for thermal treatment process in which the workpiece is heated in a vacuum atmosphere, because the color change of the workpiece is impossible in the conditions, when the workpiece is heated in a vacuum atmosphere.

Construction material of pure titanium according to the present invention manufactured in this way has a very high resistance to color change over a longer period of time compared to traditional building materials from titanium or titanium alloy.

Examples of the present invention will be described next.

Example 1

Samples

Samples No. 1-21 of high-purity titanium (5N, Purity: 99,999% or above), containing the impurity elements at predetermined values, the content of the elements and impurities, respectively, having different chemical compositions, were made to study the effect of impurity content on the color change for a long time.

Materials from raw titanium, respectively, having the chemical compositions shown in table 1, were melted in a vacuum melting furnace with valve and were obtained ingots weighing in the range from 100 to 200, the Ingot was heated by the first heating process at 1000°C for one hour, then the ingots were subjected to hot rolling by the first hot rolling process to obtain a plate thickness of 6 mm Plate thickness of 6 mm were heated by the second heating process at 1000°C for 10 minutes and by the third heating process at 850°C for one hour, the heated plate thickness of 6 mm were subjected to hot rolling by the second process of hot rolling to obtain a sheet thickness of 3 mm, These hot-rolled sheets were subjected to annealing by a process of annealing at 800°C for 10 minutes and annealed sheets of 3 mm thickness were subjected to air cooling. The scale formed on one surface of each of the annealed sheets 3 mm thick, was removed by grinding the surface to a depth of 0.5 mm, then the sheet is of a thickness of 3 mm were subjected to cold rolling through a process of cold rolling to obtain a sheet of pure titanium with a thickness of about 1 mm. Sheets of pure titanium with a thickness of approximately 1 mm were subjected to final finishing process, which was performed annealing of pure titanium with a thickness of about 1 mm under the following conditions annealing:

Temperature: 650°

The time of heating up to 650°S: 5 hours

Time: 3 hours

Vacuum: 10-6Torr

Cooling: exposed to atmosphere at 200°With or below

Test: (test resistance to color change over a long period of time.

The influence of Fe, Nb and SB as impurities on the color change for a long time has been tested by dipping sheets of pure titanium in the samples No. 1 to 21 in a solution of sulfuric acid at pH 4, heated to 60°within three days, to simulate a situation in which building materials are exposed to acid rain and the sea wind, the samples No. 1-21 were washed to remove the sulfuric acid solution remaining on the samples No. 1 to 21 fully so that the sulfuric acid solution could not contribute to the color change then the samples No. 1 to 21 were dried. Next, the color difference (ΔE*) of the samples was measured using a measuring color differences.

When determining color differences were assumed to be three-dimensional color space, the color of the sample was decomposed into three axial component ie component along one axis brightness (black/white) and two axes shades of color (red/green and yellow/blue), and the color is represented in the three-dimensional coordinates. The color difference is a difference in color between samples, represented by the distance between points defined by coordinates representing color. The smaller the color difference corresponds to less color change. When ΔE* less than 5, it is believed that the color change for a long time satisfactorily restrained. The measured data are shown in table 1, in which the underlined values are outside the range defined by the present invention.

As can be seen from table 1, samples No. 13-15, with Fe content, beyond the range of the Fe content specified by the present invention, significantly changed their color, i.e. the color differences are large. Similarly, samples 16 and 17 with the contents of Nb and Co content, beyond the range of the Nb content and the range of Co content defined by the present invention, sample No. 19 and 21, having a Nb content beyond a certain range of the content of Nb, and samples No. 18 and 20 with the content beyond a certain range of Co content, very much changed their color and have the color differences Δ E*in excess of 5, even if these models have the Fe content within a certain range of the Fe content.

On the other hand, samples No. 1-12, with the content of Fe, Nb and within a certain range of Fe, Nb and Co, are color differences ΔE* less than 5, and a high resistance to color change for a long time.

Example 2

Samples

Sheets of pure titanium with a thickness of about 1 mm in samples No. 22-45, having chemical compositions shown in table 2, were obtained from a process similar to the one through which samples have been taken No. 1-21 in example 1.

Samples No. 22 and 23 were subjected to etching instead of vacuum annealing in the last process; i.e. samples No. 22 and 23 were treated by atmospheric annealing at 700°within 20 seconds after cold rolling, immersion in salt at 550°With 15 seconds and etching to a thickness of 40 μm using a mixture, heated to 40°and containing 15 wt.% nitric acid and 1.5 wt.% hydrofluoric acid.

Test

The thickness of the surface oxide film of each of the samples was measured before immersion of the samples in a solution of sulfuric acid for testing the resistance to color change over a long period of time. More specifically, the samples were subjected to ultrasonic cleaning in acetone, the samples were yasini and oxygen concentration was measured in the following conditions:

Device: scanning auger electron spectroscope, RN (Parkin Elmer Co.)

The primary electron Energy is 5 Kev. The current 300. The angle of incidence of 30° perpendicular to the sample

The analyzed area: about 10 microns × 10 µm

The sputtering ions: Energy 3 Kev. Current 25 mA. The angle of incidence of approximately 58° perpendicular to the sample. The deposition rate of approximately 1.9 nm/min (equivalent to SiO2).

The thickness of the surface oxide film was calculated using measured data. The thickness was determined by multiplying the time of deposition (measured time)required for the oxygen concentration decreased to an average oxygen concentration between the maximum oxygen concentration and the main oxygen concentration on the deposition rate of approximately 1.9 nm/min

Color differences ΔE* samples were measured similarly after measuring the thickness of the surface oxide film. The measured data are shown in table 2.

As can be seen from table 2, the materials of pure titanium having a content of Fe, Nb and within a certain range of Fe, Nb and SB are color differences ΔE* less than 5, and a high resistance to color change for a long time.

Color differences ΔE* samples, completely finished by vacuum annealing, more than samples, finally dalannah etching. Thus, it is preferable to finally finish building materials made of pure titanium by etching.

It was found that samples having a surface oxide film thickness of not more than 170 Åare preferably small color differences ΔE* and a sufficient resistance to color change for a long time.

Example 3

Samples

Sheets of pure titanium samples No. 46-83 were produced by use of the etching process similar to that used in example 2. In samples No. 46-83 the Fe content is 0.06 or 0.03 wt.%, the Nb content is 0.001 wt.% and the content is 0.001 wt.%. The samples were subjected to final finishing by the processes of heat treatment under the conditions shown in table 3. Values 239408×X-2,3237were calculated.

Test

Color differences of samples No. 46-83 were measured similarly to the color differences of the samples in Example 1. The measured data are shown in table 4.

The measured data in table 4 demonstrate that the final finish of construction materials from pure titanium through a process of finishing, including etching and subsequent heat treatment, significantly improves the resistance to color change for a long time.

In EMA heating for heat treatment processes P, Q and R were shorter than the minimum heating time, expressed as 239408×X-2,3237and , therefore, the effect of heat treatment processes P, Q and R is slightly less. Thus, it was known that the heating time T must satisfy the expression T≥239408×X-2,3237to further improve the resistance to color change for a long time. Figure 2 shows the relationship between heating time and temperature of heating.

Despite the fact that the sample subjected to the heat treatment process S has a small color difference ΔE*, it was painted in Golden color due to heating in the atmosphere at a high temperature 280°for a long time 150 minutes Although building materials made of pure titanium, painted in such a Golden color, are appropriate when you want unpainted building material of pure titanium building materials made of pure titanium, painted in such a Golden color, have application.

Despite the fact that the color difference ΔE* sample processed through a thermal treatment process L, which is characterized by the temperature of the heating 280°and a heating time of 120 min, more than this difference in the sample treated by thermal treatment process S, the color is Alicia Δ E* satisfactorily small. The sample is processed through a thermal treatment process L, was painted less than processed through a thermal treatment process S, and was painted in Golden color.

The heating time should be 30 min or less, more preferably 10 min or less in order to prevent color change due to high temperature heating in the atmosphere.

0.001
Table 1
No. sampleThe Fe content (wt.%)The Nb content (wt.%)The Co content (wt.%)ΔE*
10.080.020.024.5
20.080.010.014.0
30.080.0050.0053.3
40.080.0010.0012.9
50.060.020.022.5
60.060.010.012.4
70.060.0050.0052.1
80.060.0011.9
90.030.020.022.2
100.030.010.012.1
110.030.0050.0051.8
120.030.0010.0011.3
130.100.0010.0019.1
140.150.0010.00114.7
150.200.0010.00118.2
160.080.030.038.9
170.030.030.036.9
180.080.0050.036.6
190.080.030.0056.3
200.030.0050.035.4
210.030.030.0055.7

The Nb content (wt.%) 41
Table 2
No. sampleThe Fe content (wt.%)The Co content (wt.%)The process of conatel. finishThe thickness of the oxide film (Å)ΔE*
220.080.020.02Etching1402.8
230.080.010.01Etching1201.6
240.080.0050.005Etching1101.2
250.080.0010.001Etching1200.8
260.060.020.02Etching1002.1
270.060.010.01Etching1301.3
280.060.0050.005Etching1601.0
290.060.0010.001Etching1500.7
300.030.020.02Etching1601.8
310.030.010.01Etching1701.1
320.030.0050,005Etching1700.8
330.030.0010.001Etching1100.6
340.080.020.02Vacuum annealing1304.5
350.080.010.01Vacuum annealing1404.0
360.080.0050.005Vacuum annealing1303.3
370.080,0010.001Vacuum annealing1502.9
380.060.020.02Vacuum annealing1502.5
390.060.010.01Vacuum annealing1602.4
400.060.0050.005Vacuum annealing1702.1
0.060.0010.001Vacuum annealing1101.9
420.030.020.02Vacuum annealing902.2
430.030.010.01Vacuum annealing802.1
440.030.0050.005Vacuum annealing1601.8
450.030.0010.001Vacuum annealing1201.3

1.1 Atmosphere
Table 3
No. sampleConditions of heating239408×X-2,3237
The temperature of the heating (°)Exposure time (min)
(A)1303 Atmosphere2.93
(In)13020 Atmosphere2.93
(C)13060 Atmosphere2.93
(D)130120 Atmosphere2.93
(E)2001.08
(F)20020 Atmosphere1.08
(G)20060 Atmosphere1.08
(H)200120 Atmosphere1.08
(1)2800.5 Atmosphere0.49
(J)28020 Atmosphere0.49
(K)28060 Atmosphere0.49
(L)280120 Atmosphere0.49
(M)130120 the Vacuum2.93
(N)200120 the Vacuum1.08
(Oh)280120 the Vacuum0.49
(R)1302 Atmosphere2.93
(Q)2000.5 Atmosphere1.08
(R)2800.2 Atmosphere0.49
(S)280150 Atmosphere0.49

Table 4
No. sampleThe Fe content (wt.%) The Mb content (wt.%)The Co content (wt.%)The process will end. finishThe heat treatment processΔE*
460.060.0010.001Etching(A)0.4
470.060.0010.001Etching(In)0.4
480.060.0010.001Etching(C)0.3
490.060.0010.001Etching(D)0.3
500.060.0010.001Etching(E)0.4
510.060.0010.001Etching(F)0.3
520.060.0010.001Etching(G)0.3
530.060.0010.001Etching(H)0.2
540.060.0010.001Etching(I)0.
550.060.0010.001Etching(J)0.3
560.060.0010.001Etching(K)0.2
570.060.0010.001Etching(L)0.2
580.060.0010.001Etching(M)0.4
590.060.0010.001Etching(N)0.3
600.060.0010.001Etching(Oh)0.3
610.030.0010.001Etching(A)0.3
620.030.0010.001Etching(In)0.2
630.030.0010.001Etching(C)0.2
640.030.0010.001Etching(D)0.2
650.03/td> 0.0010.001Etching(E)0.2
660,030.0010.001Etching(F)0.2
670.030.0010.001Etching(G)0.2
680.030.0010.001Etching(H)0.1
690.030.0010.001Etching(I)0.2
700.030.0010.001Etching(J)0.1
710.030.0010.001Etching(K)0.1
720.030.0010.001Etching(L)0.1
730.030.0010.001Etching(M)0.2
740.030.0010.001Etching(N)0.2
750.030.0010.001 Etching(Oh)0.2
760.060.0010.001Etching(R)0.7
770.060.0010.001Etching(Q)0.7
780.060.0010.001Etching(R)0.7
790.060.0010.001Etching(S)0.1
800.030.0010.001Etching(P)0.6
810.030.0010.001Etching(Q)0.6
820.030.0010.001Etching(R)0.6
830.030.0010.001Etching(S)0

1. A building material made of pure titanium, characterized in that it contains, wt%: Fe and 0.08 or less, Nb of 0.02 or less and With a 0.02 or less and has a surface oxide film thickness 170 Å or less.

2. A method of manufacturing builds the high material of pure titanium, which includes the receipt of material from pure titanium, characterized in that the material contains, wt%: Fe and 0.08 or less, Nb of 0.02 or less and 0.02, or less, then the material is OK and heated to a temperature X (° (C) in the range of 130 - 280°during the time T (min), satisfying the condition T≥239408·X-2,3237.



 

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1 tbl, 1 ex

FIELD: nonferrous metallurgy; aircraft industry; mechanical engineering; development of alloys on the basis of titanium.

SUBSTANCE: the invention is pertaining to the field of nonferrous metallurgy, in particular, to development of alloys on the base of titanium, working at the heightened temperatures. It may be used in an aircraft industry for manufacture of components, for example, disks, vanes, rings, and also in mechanical engineering. The invention presents an alloy based on titanium and a hardware product produced out of it. The alloy contains aluminum, zirconium, stannum, niobium, a molybdenum, silicon, carbon and oxygen. At that it in addition contains tungsten and iron, at the following ratio of components (in mass %): aluminum 5.8 - 6.6, zirconium 2.0 - 4.0, stannum - 2.5 - 4.5, niobium - 0.8-2.5, molybdenum - 0.8- 1.5, silicon - 0.25-0.45, carbon - 0.05-0.1, oxygen -0.05-0.12, tungsten - 0.35-0.8, iron - 0.06-0.13, titanium - the rest. The technical result is a development of an alloy having the lower weight at the given short-time strength and a specific low-cycle fatigue, that increases an operational life and reliability of the components of the hot tract of aero-engines.

EFFECT: the invention ensures development of an alloy with the lower weight at the given short-time strength and a specific low-cycle fatigue with increased operational life and reliability.

2 cl, 2 tbl, 3 ex

FIELD: non-ferrous metallurgy; methods of titanium alloy bricks production.

SUBSTANCE: the invention is pertaining to the field of non-ferrous metallurgy, in particular, to the brick made out of α+β titanium alloy and to a method of its manufacture. The offered brick consists of the following components (in mass %): aluminum - 4-5, vanadium - 2.5-3.5, iron - 1.5-2.5, molybdenum - 1.5-2.5, titanium - the rest. At that the alloy out of which the brick is manufactured, contains - 10-90 volumetric % of the primary α-phase. The average grain size of the primary α-phase makes 10 microns or less in a cross-section plain parallel to the brick rolling direction. Elongation of grain of the primary α -phase is the four-fold or less. The offered method of manufacture of the given brick includes a stage of a hot rolling. At that before the stage of the hot rolling conduct a stage of the alloy heating at the surfaces temperature (Tβ-150)- Tβ°C. During realization of the stage of the hot rolling the surface temperature is kept within the range of (Tβ-300)-( Tβ -50)°C, and the final surface temperature, that is a surface temperature directly after the last rolling, makes (Tβ-300)-( Tβ-100)°C, where Tβ is a temperature of α/β-transition. The technical result of the invention is formation of a brick out of the high-strength titanium alloy having a super pliability, excellent fatigue characteristics and moldability.

EFFECT: the invention ensures production of a brick out of the high-strength titanium alloy having a super pliability, excellent fatigue characteristics and moldability.

7 cl, 7 dwg, 21 tbl, 2 ex

FIELD: metallurgy.

SUBSTANCE: invention proposes titanium-base alloy and article made of thereof. Alloy comprising aluminum, molybdenum, vanadium, chrome, iron, zirconium, oxygen, carbon, hydrogen, nitrogen, copper and nickel comprises additionally silicon and tungsten in the following ratio of components, wt.-%: aluminum, 2.0-6.8; molybdenum, 1.0-3.5; vanadium, 3.0-6.0; chrome, 0.4-1.6; iron, 0.2-1.2; zirconium, 0.01-0.3; oxygen, 0.04-0.14; carbon, 0.02-0.1; hydrogen, 0.003-0.02; nitrogen, 0.005-0.05; copper, 0.001-0.1; nickel, 0.001-0.01; silicon, 0.02-0.15; tungsten, 0.001-0.03, and titanium, the balance. Invention provides the development of titanium alloys designated for making plane stringers, ribs, frames, fuselage, wings and engines and for applying as material for welding. Invention provides enhancing strength and crack-resistance of the basic alloy and welding joints and reducing article mass.

EFFECT: improved properties and quality of alloy.

3 cl, 2 tbl, 3 ex

FIELD: metallurgy, namely processes for forging titanium alloys and blank of such alloy suitable for forging.

SUBSTANCE: method comprises steps of preparing blank and forging it. Forging is realized at providing mechanical hardening factor equal to 1.2 or less and at difference of hardness values between central (along width) zone and near-surface zone equal to 60 or less by Vickers. Factor of mechanical hardening is determined as HV(def)/HV(ini), where HV(ini) - hardness of titanium alloy blank before forging; HV(def) -hardness of titanium alloy blank after forging at forging reduction 20%. Forging may be realized at deformation rate from 2 x 10 -4 s -1 to 1s-1 while keeping relations (T β - 400)°C ≤ Tm ≤ 900°C and 400°C ≤ Td ≤ 700°C, where Tβ (°C) -temperature of β-phase transition of titanium alloy, T m(°C) - temperature of worked blank; Td(°C) - temperature of die set. Blank has factor of mechanical hardening 1.2 or less and difference of hardness values between central (along width) zone and near-surface zone equal to 60 or less by Vickers.

EFFECT: possibility for forging titanium alloy blanks at minimum difference of material properties along depth, simplified finishing of blank surface after forging, reduced cracking of blank material, good workability of blank with favorable ductility and fatigue properties.

8 cl, 5 tbl, 6 dwg, 4 ex

FIELD: powder metallurgy, namely sintered titanium base alloys used as constructional materials.

SUBSTANCE: sintered titanium base alloy contains, mass. %: aluminum, 5.5 - 7.0; zirconium, 1.4 -2.5; molybdenum,, 0.5 - 1.8; vanadium,, 0.8 -2.3; titanium, the balance. Alloy is prepared of powder of said content with particle size in range 0.5 - 3.0 micrometers. Structure of particles includes martensite α - phase and ω-phase with coherent dissipation range 300 - 600 Å. Percentage density of alloy - 99.6%. In structure of alloy there is no α2 - phase. Alloy is prepared by compacting under pressure 1200 Mpa, sintering at 1523 K for 3 hours in vacuum 0.0133 Mpa, annealing at 723 - 823 K for 1.5 hours and cooling together with furnace until room temperature.

EFFECT: enhanced mechanical properties of alloy.

FIELD: metallurgy, in particular alloy with shape memory effect useful as implants in medicine, as temperature sensors, thermosensitive elements in equipment engineering, radio engineering, etc.

SUBSTANCE: claimed alloys contain a) (at. %) titanium 48-52; cobalt 20-30; and balance: gold; and b) titanium 48-52; iron 13,1-16; and balance: gold. Materials of present invention are free from nickel and have shape memory effect and superelasticity at human body temperatures that provides high biomechanical compatibility of implant made from the same in contacting region with various tissues of living organism.

EFFECT: alloys with excellent shape memory effect and superelasticity.

2 cl, 1 tbl, 1 ex

FIELD: mechanical engineering; piston internal combustion engines.

SUBSTANCE: invention relates to valve of internal combustion engine, method of its manufacture and heat-resistant titanium alloy used for manufacture of valve consisting of following components, mass %: aluminum 7.5-12.5; molybdenum 1.6-2.6; zirconium 1.4-2.4; silicon 0.1-0.2' yttrium 0.005-0.1; titanium - the rest. It has α+α2+β phase composition with intermetallide α2 phase on Ti3Al base dispersed in α phase. Proposed method includes forming of valve from cylindrical blank by deformation machining with preliminary heating and subsequent heat treatment. Preliminary heating of part of blank related to rod done to temperature 5-20oC lower than temperature of complete polymorphic transformation of alloy, and its deformation machining is carrying out by wedge cross rolling. Deformation machining of part of blank related to head is done by forging with preliminary heating to temperature 5-50oC higher than temperature of complete polymorphic transformation of alloy corresponding to beginning of forging, and forging is finished at temperature lower than complete polymorphic transformation of alloy to form plate head of valve and transition section provided smooth changing of head into rod. Invention provides designing of valve, method of its manufacture and heat-resistant alloy used in manufacture of valve making it possible to operate valve within operating temperature range owing to increased long-term strength and creep resistant of valve head material and increased strength, modulus of elasticity and hardness of valve rod material.

EFFECT: improved quality of valve and increased reliability in operation.

16 cl, 3 tbl, 1 ex, 15 dwg

The invention relates to the field of metallurgy, namely the creation of a modern titanium alloys used for manufacturing high-strength and high-tech products, including large, i.e

The invention relates to a method of manufacturing a rotor in the piece with the blades, which use the stub portion of the rotor is made in the preferred embodiment, titanium alloy, and are welded to her shoulder, in the preferred embodiment, also made of titanium alloy

FIELD: mechanical engineering; piston internal combustion engines.

SUBSTANCE: invention relates to valve of internal combustion engine, method of its manufacture and heat-resistant titanium alloy used for manufacture of valve consisting of following components, mass %: aluminum 7.5-12.5; molybdenum 1.6-2.6; zirconium 1.4-2.4; silicon 0.1-0.2' yttrium 0.005-0.1; titanium - the rest. It has α+α2+β phase composition with intermetallide α2 phase on Ti3Al base dispersed in α phase. Proposed method includes forming of valve from cylindrical blank by deformation machining with preliminary heating and subsequent heat treatment. Preliminary heating of part of blank related to rod done to temperature 5-20oC lower than temperature of complete polymorphic transformation of alloy, and its deformation machining is carrying out by wedge cross rolling. Deformation machining of part of blank related to head is done by forging with preliminary heating to temperature 5-50oC higher than temperature of complete polymorphic transformation of alloy corresponding to beginning of forging, and forging is finished at temperature lower than complete polymorphic transformation of alloy to form plate head of valve and transition section provided smooth changing of head into rod. Invention provides designing of valve, method of its manufacture and heat-resistant alloy used in manufacture of valve making it possible to operate valve within operating temperature range owing to increased long-term strength and creep resistant of valve head material and increased strength, modulus of elasticity and hardness of valve rod material.

EFFECT: improved quality of valve and increased reliability in operation.

16 cl, 3 tbl, 1 ex, 15 dwg

FIELD: metallurgy, in particular alloy with shape memory effect useful as implants in medicine, as temperature sensors, thermosensitive elements in equipment engineering, radio engineering, etc.

SUBSTANCE: claimed alloys contain a) (at. %) titanium 48-52; cobalt 20-30; and balance: gold; and b) titanium 48-52; iron 13,1-16; and balance: gold. Materials of present invention are free from nickel and have shape memory effect and superelasticity at human body temperatures that provides high biomechanical compatibility of implant made from the same in contacting region with various tissues of living organism.

EFFECT: alloys with excellent shape memory effect and superelasticity.

2 cl, 1 tbl, 1 ex

FIELD: powder metallurgy, namely sintered titanium base alloys used as constructional materials.

SUBSTANCE: sintered titanium base alloy contains, mass. %: aluminum, 5.5 - 7.0; zirconium, 1.4 -2.5; molybdenum,, 0.5 - 1.8; vanadium,, 0.8 -2.3; titanium, the balance. Alloy is prepared of powder of said content with particle size in range 0.5 - 3.0 micrometers. Structure of particles includes martensite α - phase and ω-phase with coherent dissipation range 300 - 600 Å. Percentage density of alloy - 99.6%. In structure of alloy there is no α2 - phase. Alloy is prepared by compacting under pressure 1200 Mpa, sintering at 1523 K for 3 hours in vacuum 0.0133 Mpa, annealing at 723 - 823 K for 1.5 hours and cooling together with furnace until room temperature.

EFFECT: enhanced mechanical properties of alloy.

FIELD: metallurgy, namely processes for forging titanium alloys and blank of such alloy suitable for forging.

SUBSTANCE: method comprises steps of preparing blank and forging it. Forging is realized at providing mechanical hardening factor equal to 1.2 or less and at difference of hardness values between central (along width) zone and near-surface zone equal to 60 or less by Vickers. Factor of mechanical hardening is determined as HV(def)/HV(ini), where HV(ini) - hardness of titanium alloy blank before forging; HV(def) -hardness of titanium alloy blank after forging at forging reduction 20%. Forging may be realized at deformation rate from 2 x 10 -4 s -1 to 1s-1 while keeping relations (T β - 400)°C ≤ Tm ≤ 900°C and 400°C ≤ Td ≤ 700°C, where Tβ (°C) -temperature of β-phase transition of titanium alloy, T m(°C) - temperature of worked blank; Td(°C) - temperature of die set. Blank has factor of mechanical hardening 1.2 or less and difference of hardness values between central (along width) zone and near-surface zone equal to 60 or less by Vickers.

EFFECT: possibility for forging titanium alloy blanks at minimum difference of material properties along depth, simplified finishing of blank surface after forging, reduced cracking of blank material, good workability of blank with favorable ductility and fatigue properties.

8 cl, 5 tbl, 6 dwg, 4 ex

FIELD: metallurgy.

SUBSTANCE: invention proposes titanium-base alloy and article made of thereof. Alloy comprising aluminum, molybdenum, vanadium, chrome, iron, zirconium, oxygen, carbon, hydrogen, nitrogen, copper and nickel comprises additionally silicon and tungsten in the following ratio of components, wt.-%: aluminum, 2.0-6.8; molybdenum, 1.0-3.5; vanadium, 3.0-6.0; chrome, 0.4-1.6; iron, 0.2-1.2; zirconium, 0.01-0.3; oxygen, 0.04-0.14; carbon, 0.02-0.1; hydrogen, 0.003-0.02; nitrogen, 0.005-0.05; copper, 0.001-0.1; nickel, 0.001-0.01; silicon, 0.02-0.15; tungsten, 0.001-0.03, and titanium, the balance. Invention provides the development of titanium alloys designated for making plane stringers, ribs, frames, fuselage, wings and engines and for applying as material for welding. Invention provides enhancing strength and crack-resistance of the basic alloy and welding joints and reducing article mass.

EFFECT: improved properties and quality of alloy.

3 cl, 2 tbl, 3 ex

FIELD: non-ferrous metallurgy; methods of titanium alloy bricks production.

SUBSTANCE: the invention is pertaining to the field of non-ferrous metallurgy, in particular, to the brick made out of α+β titanium alloy and to a method of its manufacture. The offered brick consists of the following components (in mass %): aluminum - 4-5, vanadium - 2.5-3.5, iron - 1.5-2.5, molybdenum - 1.5-2.5, titanium - the rest. At that the alloy out of which the brick is manufactured, contains - 10-90 volumetric % of the primary α-phase. The average grain size of the primary α-phase makes 10 microns or less in a cross-section plain parallel to the brick rolling direction. Elongation of grain of the primary α -phase is the four-fold or less. The offered method of manufacture of the given brick includes a stage of a hot rolling. At that before the stage of the hot rolling conduct a stage of the alloy heating at the surfaces temperature (Tβ-150)- Tβ°C. During realization of the stage of the hot rolling the surface temperature is kept within the range of (Tβ-300)-( Tβ -50)°C, and the final surface temperature, that is a surface temperature directly after the last rolling, makes (Tβ-300)-( Tβ-100)°C, where Tβ is a temperature of α/β-transition. The technical result of the invention is formation of a brick out of the high-strength titanium alloy having a super pliability, excellent fatigue characteristics and moldability.

EFFECT: the invention ensures production of a brick out of the high-strength titanium alloy having a super pliability, excellent fatigue characteristics and moldability.

7 cl, 7 dwg, 21 tbl, 2 ex

FIELD: nonferrous metallurgy; aircraft industry; mechanical engineering; development of alloys on the basis of titanium.

SUBSTANCE: the invention is pertaining to the field of nonferrous metallurgy, in particular, to development of alloys on the base of titanium, working at the heightened temperatures. It may be used in an aircraft industry for manufacture of components, for example, disks, vanes, rings, and also in mechanical engineering. The invention presents an alloy based on titanium and a hardware product produced out of it. The alloy contains aluminum, zirconium, stannum, niobium, a molybdenum, silicon, carbon and oxygen. At that it in addition contains tungsten and iron, at the following ratio of components (in mass %): aluminum 5.8 - 6.6, zirconium 2.0 - 4.0, stannum - 2.5 - 4.5, niobium - 0.8-2.5, molybdenum - 0.8- 1.5, silicon - 0.25-0.45, carbon - 0.05-0.1, oxygen -0.05-0.12, tungsten - 0.35-0.8, iron - 0.06-0.13, titanium - the rest. The technical result is a development of an alloy having the lower weight at the given short-time strength and a specific low-cycle fatigue, that increases an operational life and reliability of the components of the hot tract of aero-engines.

EFFECT: the invention ensures development of an alloy with the lower weight at the given short-time strength and a specific low-cycle fatigue with increased operational life and reliability.

2 cl, 2 tbl, 3 ex

FIELD: medicine; instrument-making industry; radio industry; production of materials with a memory effect of the form.

SUBSTANCE: the invention is pertaining to the materials with a memory effect of the form and with the modified surface, which may be used as implants in medicine and as the temperature sensors, thermo-sensitive and executive elements and designs in instrument-making industry, the radio industry. The offered material consists of a base made out of a titanium nickelide of the following composition (in at. %): titanium - 49-51, nickel - the rest, and the surface layer modified by alloying elements. The modified surface layer is formed by irradiation with a low-energy high-current electronic beam and has a depth of 1000-2500 nanometers and the dimensions of the crystal grains of no more than 30 nanometers. In the capacity of the alloying elements it contains oxygen and carbon at the following ratio of components (in at. %): oxygen - 10-20, carbon - 10-15, titanium - 40-50, nickel - the rest. The technical result of the invention is production of the materials with an effect of memory of the form and a high degree capability of the form restoration both at a low and high deforming loadings.

EFFECT: the invention ensures production of the materials with an effect of memory of the form and a high degree capability of the form restoration both at a low and high deforming loadings.

1 tbl, 1 ex

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