CN1216164C - Titanium alloy coated mould material for photographic trade and manufacturing method thereof - Google Patents

Abstract

The invention relates to a titanium alloy material, in particular to a titanium alloy coating mold material used in the photographic industry and a manufacturing method thereof. The chemical composition (weight percentage) of the titanium alloy coating mold material is Ti-based; Al: 5.0% to 7.0 %; Fe: 1.3% to 2.2%; C: 0 to 0.05%; N: 0 to 0.035%; H: 0 to 0.0125%; O: 0 to 0.15%. ～950℃/30min～90min/WQ, become a soft material that is easy to machine, its hardness HRC≤37.2; after processing into blank parts, aging heat treatment: 450℃～550℃/6h～12h/AC, its hardness HRC≥ 40. The titanium alloy coating mold material of the present invention not only has strong corrosion resistance in various media, especially high silver chloride emulsion, but also does not affect the photographic performance, and is suitable for the production of coating molds and various storage equipment in the photographic industry, etc. , the titanium alloy material provided by the invention does not contain rare and precious metals and has market competitiveness.

Description

A kind of titanium alloy coating mold material and manufacturing method for photographic industry

Technical field:

The invention relates to a titanium alloy material, in particular to a titanium alloy coating mold material used in the photographic industry and a manufacturing method thereof.

technical background:

Coating dies in the photographic industry are a central component of the emulsion coating process. In recent years, a variety of coating molds made of stainless steel have been used in China, but they are not ideal in practical applications. This is because the photosensitive emulsion contains highly corrosive halides. Experiments have confirmed that 0Cr14NiMn3Al is placed in the photosensitive emulsion solution. After hours, there will be leaf-shaped corrosion marks, which not only change the geometry of the coating mold, affect the coating effect and reduce the service life of the coating mold, but also corrode products are brought into the photosensitive coating layer to affect the photographic performance. At present, the SUS317 stainless steel (Japanese standard) used in the production of coating molds abroad has low hardness (HB146), high requirements for material process control, easy to scratch when used, and difficult to process and manufacture. In addition, the cleaning of the coating system Most of the liquid is a strong oxidizing agent, such as NaClO, and the coating mold is easily oxidized. Although the corrosion resistance of pure titanium is satisfactory, due to the low hardness of pure titanium, the processing accuracy is not easy to control, and the surface is easily scratched, which will lead to coating problems, so it cannot meet the use requirements. Chinese patent CN1170767A discloses a titanium alloy material. Although the material has excellent corrosion resistance, it contains Cu element, which is not suitable for making photographic emulsion equipment. Thereby it is necessary to develop a new coating mold material that can satisfy the photographic industry.

Invention content:

The object of the present invention is to provide a titanium alloy material for coating molds in the photographic industry and a manufacturing method of the material. The coating molds for the photographic industry made of this material have satisfactory corrosion resistance and do not affect photosensitivity. The performance of the emulsion and the characteristics of high hardness can meet the special requirements of various storage equipment in the production of photographic emulsion coating molds and feeding systems.

Technical scheme of the present invention is:

A titanium alloy coating mold material for the photographic industry, characterized in that: the chemical composition (weight percentage) of the material is Ti-based; Al: 5.0% to 7.0%; Fe: 1.3% to 2.2%; C: 0 to 0.05% %; N: 0-0.035%; H: 0-0.0125%; O: 0-0.15%; which does not contain Cu, Zn, Sn, Pb and other elements that affect the photographic emulsion.

A method for producing a titanium alloy coating mold material for the photographic industry, comprising:

a. Use zero-grade sponge titanium, industrial pure iron, industrial pure aluminum foil, and aluminum strips as raw materials, make ingredients according to the chemical composition of the alloy, and press the electrodes;

b. The pressed electrode is argon-arc welded under vacuum or argon protection, and then melted twice in a vacuum consumable electric arc furnace and cast into an alloy ingot;

c. Heat the alloy ingot in an electric furnace and then forge the billet. The temperature of the forging billet is controlled between 1050°C and 1150°C;

d. Heat the semi-finished product that has been forged and opened in an electric furnace for thermal processing. The thermal processing temperature is controlled between 850°C and 950°C. The first deformation of the semi-finished product should be greater than 60%. The remaining fire deformation of the finished bar or profile is not less than 40%. During the period, deformation in the temperature zone above the α+β/β phase transition is carried out, the deformation amount is not less than 30%, and this cycle is not less than two times; if the plate is produced, the deformation amount of each fire is not less than 50%, and the deformation amount of the last fire Not less than 60%;

It is characterized in that: the rod or profile made by thermal processing is processed and formed in the state of solid solution treatment, the material hardness HRC≤37.2, the solid solution heat treatment system is: 850℃～950℃/30min～90min/WQ, after processing and forming , and then used after aging treatment, material hardness HRC ≥ 40, the aging heat treatment system is: 480 ℃ ~ 530 ℃ / 6h ~ 12h / AC.

By adopting the above-mentioned technical scheme, the present invention fully satisfies the application in various media environments in the photographic industry, especially in high-corrosion environments of high-silver chloride emulsion, and the material has high hardness. It can be used to produce coating molds, feeding devices and various storage equipment for the photographic industry.

Detailed ways

The present invention will be further described below by specific examples.

Example 1:

A production method for coating mold materials with titanium alloys in the photographic industry, comprising: adopting zero-grade sponge titanium, industrial pure iron, industrial pure aluminum foil, aluminum strips, according to (weight percentage) Al: 5.7%, Fe: 1.9%, at the same time Control the oxygen content and other impurity content within the required range, and press the electrode; the pressed electrode is argon-arc welded under vacuum or argon protection, and it is melted twice in a vacuum consumable electric arc furnace and cast into an alloy ingot ;Heat the alloy ingot in an electric furnace and then carry out billet forging, and the temperature of the billet forging is controlled at 1150°C; put the semi-finished product that has been forged and billeted in an electric furnace and then heat it, and then carry out thermal processing, and the thermal processing temperature is controlled at 900°C; The first deformation of the semi-finished product thermal processing is 70%, and the remaining heat deformation is 45%. During this period, the temperature zone above the α+β/β phase transformation is deformed, and the deformation is 35%. This cycle is carried out three times, and finally it is made Bars; for heat treatment of bars made by thermal processing, the solid solution heat treatment system is: 850°C/30min/WQ, at this time the hardness HRC value of the material is 34.5; after processing and forming, it is used after aging treatment, and its The aging heat treatment system is: 480°C/8h/AC. At this time, the hardness HRC value of the material is 42. Sample 1 is obtained. The composition of the sample is analyzed, and the results are shown in Table 1.

Example 2:

Use zero-grade sponge titanium, industrial pure iron, industrial pure aluminum foil, aluminum strip, according to (weight percentage) Al: 7.0%, Fe: 1.3%, at the same time control the content of oxygen and other impurities within the required range, and press the electrode; The pressed electrodes are welded by argon arc under vacuum or argon protection, and cast into alloy ingots after being smelted twice in a vacuum consumable electric arc furnace; The forging temperature is controlled at 1050°C; the semi-finished product that has been forged and opened is heated in an electric furnace for thermal processing, and the thermal processing temperature is controlled at 950°C; the first deformation of the semi-finished product is 65%, and the remaining heat deformation is 40%, during which the temperature zone above the α+β/β phase transformation is deformed, and the deformation amount is 30%. This cycle is carried out twice, and finally made into bars; The heat treatment system is: 950℃/50min/WQ, at this time the hardness HRC value of the material is 37.2; after processing and molding, it is used after aging treatment, and the aging heat treatment system is: 530℃/6h/AC, the hardness of the material at this time HRC value is 42.5, obtains sample 2, carries out component analysis to sample, and the results are shown in Table 1.

Example 3:

Use zero-grade sponge titanium, industrial pure iron, industrial pure aluminum foil, aluminum strip, according to (weight percentage) Al: 5.0%, Fe: 2.2%, at the same time control the content of oxygen and other impurities within the required range, and press the electrode; The pressed electrodes are welded by argon arc under vacuum or argon protection, and cast into alloy ingots after being smelted twice in a vacuum consumable electric arc furnace; The forging temperature is controlled at 1100°C; the slab is placed in a resistance furnace, the heating temperature is controlled at 850°C, and it is rolled with two fires in a 200-ton vacuum rolling mill. The deformation in the first fire is 65%, and the deformation in the last fire is 80%. %, finally get the sheet. For heat treatment of the plate made by thermal processing, the solid solution heat treatment system is: 910°C/90min/WQ, at this time, the hardness HRC value of the material is 36.7; after processing and forming, it is used after aging treatment, and the aging heat treatment system is : 520°C/12h/AC. At this time, the hardness HRC value of the material is 42.8. Sample 3 is obtained. The composition of the sample is analyzed, and the results are shown in Table 1.

Corrosion resistance example 1: Take the same piece of the above sample 1, polish each surface with sandpaper, clean it with deionized water and alcohol, dry it at 100°C for 2 hours, cool it, and soak it in green emulsion fully and half soaked respectively. For the samples, the immersion times were 144 hours, 316 hours and 544 hours, respectively. After cleaning the corroded samples (HF:HNO ₃ :H ₂ O=1:3:7), the samples were analyzed by metallographic observation (OLYMPUS), scanning electron microscope (JSM-5800) and energy spectrometer (LINK ISIS). It is found that the alloy corrodes slowly, about 0.000mm/a-0.0107mm/a is an extremely corrosion-resistant material, and the uniform corrosion resistance rate is shown in Attached Table 4.

Corrosion resistance example 2: Yellow emulsion is the most corrosive among photosensitive emulsions, and half immersion is more corrosive than full immersion. This embodiment adopts half immersion corrosion experiment. Grind each side of the above-mentioned sample 2 with abrasive paste, clean with deionized water and alcohol, dry at 100°C for 2 hours, cool, soak the sample in yellow emulsion for 144 hours, and use protease solution at room temperature Take it out after submerging for 1 hour, clean the corroded sample, and carry out metallographic observation, scanning electron microscope and energy spectrum analysis. It is found that the alloy corrodes slowly, about 0.03mm/a-0.04mm/a is an extremely corrosion-resistant material, and the uniform corrosion resistance rate is shown in Attached Table 4.

Corrosion resistance example 3: Take the same piece of the above sample 3, make it clean and dry, weigh it, and take another dual-phase steel sample of the same size and weight, and soak it fully and half in NaClO (0.8% W) solution and NaOH (0.4% W) respectively. %W) solution, control the temperature at 40.2°C, soak for 6 hours, 8 hours and 12 hours respectively, take out, wash, dry and weigh, and observe the surface corrosion. The test results are shown in attached table 4.

Example 4 of crevice corrosion resistance: Take the same piece of the above sample 1. After the sample is heat-treated, first grind off the scale of the sample, then drill a Φ100mm hole in the middle of the sample, use sandpaper to polish all sides of the sample, and use deionized water , alcohol cleaning, drying and cooling, tighten the two samples with pure titanium bolts, separate the samples with two titanium sheets of δ0.2mm×1mm×15mm, make a gap of 0.2mm, and put the samples into The yellow emulsion was taken out after soaking for 144, 480, and 984 hours, and the surface scanning electron microscope and energy spectrum analysis were carried out. It was found that no obvious corrosion occurred after soaking for 144 hours.

Electrochemical Corrosion Resistance Example 5: Take a sample of the above-mentioned sample 1, and the electrochemical corrosion in the emulsion is shown in attached table 4.

Photographic performance test example: Take sample 1 with a size of 20mm×20mm×2mm and grind it, soak it in SA-2 colored paper yellow emulsion, soak it at 42°C for 0 hour, 3 hours, 6 hours and 9 hours respectively, and coat Observing the change of the fog in the film ring, it is found that the influence of the material on the photographic performance is minimal. The test data are shown in attached table 3.

Attached Table 1: Analysis data of the composition of the titanium alloy material of the present invention Type of experiment Ti(%) Al(%) Fe(%) C(%) N(%) H(%) O(%) sample 1 92.1676 5.7 1.9 0.05 0.03 0.0124 0.14 sample 2 91.4565 7 1.3 0.048 0.033 0.0125 0.15 sample 3 92.5647 5 2.2 0.049 0.034 0.0123 0.14

Attached Table 2: Experimental data on hardness of titanium alloy of the present invention Type of experiment Experimental results Remark sample 1 HRC value after solid solution treatment HCR value after aging treatment Stablize 34.5 40 sample 2 HRC value after solid solution treatment HCR value after aging treatment Stablize 37.2 42.5 sample 3 HRC value after solid solution treatment HCR value after aging treatment Stablize 36.7 42.8

Attached Table 3: Photographic Performance Experimental Data

Attached Table 4: Experimental Data of Corrosion Resistance of Titanium Alloy Materials of the Invention in Various Media Type of test test results Remark Green Emulsion Corrosion Test 114(h) 316(h) 554(h) extremely corrosion resistant material Corrosion rate(mm/a) Average corrosion rate (mm/a) Corrosion rate(mm/a) Average corrosion rate (mm/a) Corrosion rate(mm/a) Average corrosion rate (mm/a) 0.00000.00000.0000 0.0000 0.01120.01120.0075 0.0010 0.00640.01070.0107 0.0093 Corrosion resistance test of yellow emulsion 114(h) extremely corrosion resistant material Corrosion rate(mm/a) Average corrosion rate (mm/a) 0.03350.0337 0.0336 Corrosion resistance experiment of titanium alloy and dual-phase steel material type Corrosive solution Full immersion (40.2) (h) Semi-immersion (40.2) (h) Semi-immersion (30.0) (h) 0.0093 Semi-soaked weight (g) Semi-soaked weight (g) Phenomenon Titanium alloys are more resistant to oxidation than duplex steels Before dipping After soaking Before dipping After soaking Before dipping After soaking Titanium alloy NaCLO 6 8 12 6.5 6.5 6.5 6.5 6.5 6.5 no corrosion Titanium alloy NaOH 6 8 12 6.3 6.3 6.3 6.3 6.3 6.3 no corrosion biphasic NaCLO 6 8 12 After half immersion at 40.2°C for 3 hours, an iron-red substance precipitated at the gas-liquid boundary. Component Analysis of Gap Test Area Elemental Ti (weight percent) Element Al (weight percent) Element Fe (weight percent) Total weight % Alloy Composition 92.4 5.7 1.9 100 Electrochemical corrosion Corrosion potential (V) Corrosion current (A/cm ² ) Thermodynamically difficult to corrode 0.41 ^10-5

It can be seen from the data in the table that the hardness and corrosion resistance of the titanium alloy material of the present invention not only meet the special requirements of the photographic industry in various media, especially in high silver chloride emulsions, but also do not affect the photographic performance.

Claims (3)

1. A titanium alloy coating mold material for the photographic industry, characterized in that: the weight percentage of the chemical composition of the material is: Al: 5.0% to 7.0%; Fe: 1.3% to 2.2%; C: 0 to 0.05% ; N: 0-0.035%; H: 0-0.0125%; O: 0-0.15%; the balance is pure Ti. 2. According to claim 1, the titanium alloy coating mold material for the photographic industry is characterized in that, wherein said titanium alloy coating mold material is used for producing coating nozzles, feeding devices and various storage equipment for the photographic industry. 3. a kind of production method of titanium alloy coating mold material for photographic industry according to claim 1, comprising: a. Use zero-grade sponge titanium, industrial pure iron, industrial pure aluminum foil, and aluminum strips as raw materials, make ingredients according to the chemical composition of the alloy, and press the electrodes; b. The pressed electrode is argon-arc welded under vacuum or argon protection, and then melted twice in a vacuum consumable electric arc furnace and cast into an alloy ingot; c. Heat the alloy ingot in an electric furnace and then forge the billet. The temperature of the forging billet is controlled between 1050°C and 1150°C; d. Heat the semi-finished product that has been forged and opened in an electric furnace for thermal processing. The thermal processing temperature is controlled between 850°C and 950°C. The first deformation of the semi-finished product should be greater than 60%. The rest of the deformation of the finished bar or profile is not less than 40%, during which the temperature zone above the α+β/β phase transformation is deformed, the deformation is not less than 30%, and this cycle is not less than two times; if the plate is produced, The deformation amount of each fire is not less than 50%, and the deformation amount of the last fire is not less than 60%; It is characterized in that: the rod or profile made by thermal processing is processed and formed in the state of solid solution treatment, the material hardness HRC≤37.2, the solid solution heat treatment system is: 850℃～950℃/30min～90min/WQ, after processing and forming , and then used after aging treatment, material hardness HRC ≥ 40, the aging heat treatment system is: 480 ℃ ~ 530 ℃ / 6h ~ 12h / AC.