CN103710649A - Carbon fiber reinforced titanium alloy composite material and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明涉及一种碳纤维增强钛合金复合材料的制备方法，包含如下步骤：准备钛合金，碳纤维预处理，镀镍，沉积铬，将钛合金粉末均匀铺在模具内，然后在钛合金粉末层上排列剪好的镀层碳纤维，然后再铺设一层钛合金粉末，重复上述过程至模具填满，对粉体实施加压加热操作，在真空炉内进行烧结，冷却得到的烧结体即得到该碳纤维增强钛合金复合材料。该复合材料具有强度极高的技术效果。The invention relates to a method for preparing a carbon fiber-reinforced titanium alloy composite material, which comprises the following steps: preparing titanium alloy, carbon fiber pretreatment, nickel plating, chromium deposition, evenly spreading titanium alloy powder in a mould, and then spreading the titanium alloy powder on the titanium alloy powder layer Arrange the cut coated carbon fibers, then lay a layer of titanium alloy powder, repeat the above process until the mold is filled, pressurize and heat the powder, sinter in a vacuum furnace, and cool the obtained sintered body to obtain the carbon fiber reinforcement. Titanium alloy composite. The composite material has a technical effect of extreme strength.

Description

A kind of carbon fiber strengthens titanium alloy composite material and preparation method thereof

Technical field

The invention belongs to alloy composite materials field, particularly relate to a kind of carbon fiber and strengthen titanium alloy composite material and preparation method thereof.

Background technology

Carbon fiber strengthens titanium alloy composite material and is composited by the carbon fiber that has the titanium alloy of high specific strength and have high ratio modulus, a stretch-proof, has that density is low, specific tenacity is high, stretch-proof and a specific modulus advantages of higher.Its mechanical property can be carried out the adjustment in certain limit by adjusting the distribution of carbon fiber in titanium alloy and the control of titanium alloy component, is a kind of high performance lightweight structural material.

Summary of the invention

One of object of the present invention is to propose the preparation method that a kind of carbon fiber strengthens titanium alloy composite material;

Two of object of the present invention is to propose a kind of carbon fiber and strengthens titanium alloy composite material;

For reaching this object, the present invention by the following technical solutions:

Carbon fiber strengthens a preparation method for titanium alloy composite material, comprises following steps:

(1) prepare titanium alloy, described titanium alloy is grouped into by following one-tenth according to weight percentage: Nb:25 ~ 32%, and Zr:6 ~ 8.1%, Sn:11 ~ 16.2%, O:0.01 ~ 0.18%, RE:1.8 ~ 2.6%, Al:3.2 ~ 4.2%, surplus is Ti;

(2) carbon fiber remove photoresist, neutralize, activation, reduction pretreatment;

(3) at carbon fiber surface, carry out chemical nickel plating;

(4) the nickel-coated carbon fibers surface chemistry deposition layer of metal chromium obtaining in step (3) after cleaning-drying;

(5) plated carbon fiber step (4) being obtained is cut into the length of 1 ~ 20mm;

(6) by the titanium alloys powdered of step (1), by titanium alloy powder uniform spreading in mould, thickness is 1 ~ 5cm, then the plated carbon fiber that alignment step (5) shears on titanium alloy powder layer, and then laying one deck titanium alloy powder, thickness is 1 ~ 5mm, repeats said process to mould and fills up;

(8) powder is implemented to pressurized, heated operation, temperature is 100 ~ 160 ℃, and pressure is 560 ~ 800MPa, and the dwell time is 10 ~ 180s;

(9) in vacuum oven, carry out sintering, sintering temperature is 1000 ~ 1450 ℃, and the sintered heat insulating time is 1 ~ 6h;

(10) the sintered compact that cooling step (9) obtains obtains this carbon fiber and strengthens titanium alloy composite material;

Described titanium alloy is made by following steps:

(a) batching: according to Nb:25 ~ 32%, Zr:6 ~ 8.1%, Sn:11 ~ 16.2%, O:0.01 ~ 0.18%, RE:1.8 ~ 2.6%, Al:3.2 ~ 4.2%, surplus is that Ti prepares burden, wherein Ti is with titanium sponge, and Zr adopts Ti-52Nb master alloy, Sn to adopt Ti-68Sn master alloy, RE to adopt mishmetal, Al to adopt Ti-Al master alloy with zirconium sponge, Nb, and O is relict element in above-mentioned raw materials;

(b) melting: the material that step (a) is prepared is pressed into electrode, in vacuum consumable electrode arc furnace, melting is 2 times;

(c) homogenizing annealing: homogenization temperature is 980 ~ 1200 ℃, and the hold-time is 10 ~ 18h, removal zone of oxidation strips off the skin after annealing;

(d) forge: Forge Heating temperature is 920 ~ 980 ℃, and soaking time is 68 ~ 86min, and final forging temperature is 810 ~ 860 ℃;

(e) hot rolling: process annealing is not carried out in rolling, rolling pass is 8;

(f) cold rolling: cold rolling total deformation is 80%;

(g) solution heat treatment: cold-reduced sheet is carried out in chamber type electric resistance furnace to solution heat treatment, solid solubility temperature is 835-860 ℃, and soaking time is 0.8-1.8h, shrend;

(h) timeliness thermal treatment: be divided into following four steps: aging temp is 300 ~ 320 ℃, soaking time is 5 ~ 18min, shrend; Carry out ageing treatment for the second time being heated to 400 ~ 420 ℃, aging time is 1 ~ 1.8h, shrend; Reheat 480 ~ 495 ℃ and carry out timeliness for the third time, aging time is 2 ~ 2.5h, shrend; Reheat 520 ~ 550 ℃ and carry out timeliness the 4th time, aging time is 5 ~ 8h, shrend; Obtain titanium alloy finished product.

As preferably, described carbon fiber removes photoresist to process and adopts air calcination method to carry out.

As preferably, described carbon fiber neutralizing treatment adopts KOH or ammoniacal liquor to neutralize.

As preferably, described carbon fiber activation treatment adopts PdCl₂with AgCl be activation solution.

As preferably, in titanium alloy preparation process, timeliness thermal treatment is divided into following four steps: aging temp is 310 ℃, and soaking time is 8min, shrend; Reheat 420 ℃ and carry out ageing treatment for the second time, aging time is 1h, shrend; Reheat 485 ℃ and carry out timeliness for the third time, aging time is 2h, shrend; Reheat 535 ℃ and carry out timeliness the 4th time, aging time is 5h, shrend.

As preferably, described titanium alloy is grouped into by following one-tenth according to weight percentage: Nb:28%, and Zr:6.8%, Sn:15.2%, O:0.15%, RE:2.1%, Al:3.8%, surplus is Ti.

Carbon fiber strengthens a titanium alloy composite material, it is characterized in that, adopts preceding method to make.

effect of the present invention is:

Titanium alloy by specific specific concrete carbon fiber and concrete component content coordinates, and final composite property is largely increased;

By heat treated cooperations such as concrete timeliness thermal treatment and concrete solid solutions, make to there is high strength as the titanium alloy of matrix, high elastic coefficient, the elongation of becoming reconciled and fracture toughness property, finally cause end properties high;

By the restriction of above-mentioned concrete preparation method's parameter and coordinating of concrete alloying constituent, stability has been reached more than 90%.

Embodiment

embodiment 1

Carbon fiber strengthens a preparation method for titanium alloy composite material, comprises following steps:

(1) prepare titanium alloy, described titanium alloy is grouped into by following one-tenth according to weight percentage: Nb:28%, and Zr:6.9%, Sn:15.2%, O:0.10%, RE:1.99%, Al:3.82%, surplus is Ti;

(2) carbon fiber remove photoresist, neutralize, activation, reduction pretreatment;

(3) at carbon fiber surface, carry out chemical nickel plating;

(4) the nickel-coated carbon fibers surface chemistry deposition layer of metal chromium obtaining in step (3) after cleaning-drying;

(5) plated carbon fiber step (4) being obtained is cut into the length of 18mm;

(6), by the titanium alloys powdered of step (1), by titanium alloy powder uniform spreading, in mould, thickness is 4cm, then the plated carbon fiber that alignment step (5) shears on titanium alloy powder layer, and then lay one deck titanium alloy powder, thickness is 4mm, repeats said process to mould and fills up;

(8) powder is implemented to pressurized, heated operation, temperature is 150 ℃, and pressure is 700MPa, and the dwell time is 98s;

(9) in vacuum oven, carry out sintering, sintering temperature is 1100 ℃, and the sintered heat insulating time is 4h;

(10) the sintered compact that cooling step (9) obtains obtains this carbon fiber and strengthens titanium alloy composite material;

Described titanium alloy is made by following steps:

(a) batching: according to Nb:28%, Zr:6.9%, Sn:15.2%, O:0.10%, RE:1.99%, Al:3.82%, surplus is that Ti prepares burden, wherein Ti is with titanium sponge, and Zr adopts Ti-52Nb master alloy, Sn to adopt Ti-68Sn master alloy, RE to adopt mishmetal, Al to adopt Ti-Al master alloy with zirconium sponge, Nb, and O is relict element in above-mentioned raw materials;

(b) melting: the material that step (a) is prepared is pressed into electrode, in vacuum consumable electrode arc furnace, melting is 2 times;

(c) homogenizing annealing: homogenization temperature is 990 ℃, and the hold-time is 12h, removal zone of oxidation strips off the skin after annealing;

(d) forge: Forge Heating temperature is 960 ℃, and soaking time is 69min, and final forging temperature is 820 ℃;

(e) hot rolling: process annealing is not carried out in rolling, rolling pass is 8;

(f) cold rolling: cold rolling total deformation is 80%;

(g) solution heat treatment: cold-reduced sheet is carried out in chamber type electric resistance furnace to solution heat treatment, solid solubility temperature is 845 ℃, and soaking time is 0.9h, shrend;

(h) timeliness thermal treatment: be divided into following four steps: aging temp is 310 ℃, soaking time is 12min, shrend; Carry out ageing treatment for the second time being heated to 410 ℃, aging time is 1h, shrend; Reheat 480 ℃ and carry out timeliness for the third time, aging time is 2h, shrend; Reheat 520 ℃ and carry out timeliness the 4th time, aging time is 5h, shrend; Obtain titanium alloy finished product.

embodiment 2:

Carbon fiber strengthens a preparation method for titanium alloy composite material, comprises following steps:

(1) prepare titanium alloy, described titanium alloy is grouped into by following one-tenth according to weight percentage: Nb:28%, and Zr:6.8%, Sn:15.2%, O:0.15%, RE:2.1%, Al:3.8%, surplus is Ti;

Described titanium alloy is made by following steps:

(a) batching: according to Nb:28%, Zr:6.8%, Sn:15.2%, O:0.15%, RE:2.1%, Al:3.8%, surplus is that Ti prepares burden, wherein Ti is with titanium sponge, and Zr adopts Ti-52Nb master alloy, Sn to adopt Ti-68Sn master alloy, RE to adopt mishmetal, Al to adopt Ti-Al master alloy with zirconium sponge, Nb, and O is relict element in above-mentioned raw materials;

(b) melting: the material that step (a) is prepared is pressed into electrode, in vacuum consumable electrode arc furnace, melting is 2 times;

(c) homogenizing annealing: homogenization temperature is 990 ℃, and the hold-time is 12h, removal zone of oxidation strips off the skin after annealing;

(d) forge: Forge Heating temperature is 960 ℃, and soaking time is 69min, and final forging temperature is 820 ℃;

(e) hot rolling: process annealing is not carried out in rolling, rolling pass is 8;

(f) cold rolling: cold rolling total deformation is 80%;

(g) solution heat treatment: cold-reduced sheet is carried out in chamber type electric resistance furnace to solution heat treatment, solid solubility temperature is 845 ℃, and soaking time is 0.9h, shrend;

(h) timeliness thermal treatment: be divided into following four steps: aging temp is 310 ℃, soaking time is 8min, shrend; Reheat 420 ℃ and carry out ageing treatment for the second time, aging time is 1h, shrend; Reheat 485 ℃ and carry out timeliness for the third time, aging time is 2h, shrend; Reheat 535 ℃ and carry out timeliness the 4th time, aging time is 5h, and shrend obtains titanium alloy finished product.

(2) carbon fiber remove photoresist, neutralize, activation, reduction pretreatment; Carbon fiber removes photoresist to process and adopts air calcination method to carry out; Carbon fiber neutralizing treatment adopts ammoniacal liquor to neutralize; Carbon fiber activation treatment adopts PdCl₂with AgCl be activation solution.

(3) at carbon fiber surface, carry out chemical nickel plating;

(4) the nickel-coated carbon fibers surface chemistry deposition layer of metal chromium obtaining in step (3) after cleaning-drying;

(5) plated carbon fiber step (4) being obtained is cut into the length of 18mm;

(6), by the titanium alloys powdered of step (1), by titanium alloy powder uniform spreading, in mould, thickness is 4cm, then the plated carbon fiber that alignment step (5) shears on titanium alloy powder layer, and then lay one deck titanium alloy powder, thickness is 4mm, repeats said process to mould and fills up;

(8) powder is implemented to pressurized, heated operation, temperature is 150 ℃, and pressure is 700MPa, and the dwell time is 98s;

(9) in vacuum oven, carry out sintering, sintering temperature is 1100 ℃, and the sintered heat insulating time is 4h;

(10) the sintered compact that cooling step (9) obtains obtains this carbon fiber and strengthens titanium alloy composite material.

Claims (7)

Translated fromChinese

1.一种碳纤维增强钛合金复合材料的制备方法，其特征在于，包含如下步骤：1. a preparation method of carbon fiber reinforced titanium alloy composite material, is characterized in that, comprises the steps:（1）准备钛合金，所述钛合金按照重量百分含量由如下成分组成：Nb：25~32%，Zr：6~8.1%，Sn：11~16.2%，O：0.01~0.18%，RE：1.8~2.6%，Al：3.2~4.2%，余量为Ti；(1) Prepare a titanium alloy, the titanium alloy is composed of the following components according to the weight percentage: Nb: 25~32%, Zr: 6~8.1%, Sn: 11~16.2%, O: 0.01~0.18%, RE : 1.8~2.6%, Al: 3.2~4.2%, the balance is Ti;（2）碳纤维去胶、中和、活化、还原预处理；(2) Carbon fiber degumming, neutralization, activation, reduction pretreatment;（3）在碳纤维表面进行化学镀镍；(3) Electroless nickel plating on the carbon fiber surface;（4）清洗干燥后在步骤（3）得到的镀镍碳纤维表面化学沉积一层金属铬；(4) chemically depositing a layer of metal chromium on the surface of the nickel-plated carbon fiber obtained in step (3) after cleaning and drying;（5）将步骤（4）得到的镀层碳纤维剪成1~20mm的长度；(5) Cut the coated carbon fiber obtained in step (4) into a length of 1 to 20 mm;（6）将步骤（1）的钛合金制成粉末，将钛合金粉末均匀铺在模具内，厚度为1~5cm，然后在钛合金粉末层上排列步骤（5）剪好的镀层碳纤维，然后再铺设一层钛合金粉末，厚度为1~5mm，重复上述过程至模具填满；(6) Make the titanium alloy in step (1) into powder, evenly spread the titanium alloy powder in the mold with a thickness of 1~5cm, and then arrange the coated carbon fiber cut in step (5) on the titanium alloy powder layer, and then Then lay a layer of titanium alloy powder with a thickness of 1~5mm, repeat the above process until the mold is filled;（8）对粉体实施加压加热操作，温度为100~160℃，压力为560~800MPa，保压时间为10~180s；(8) Pressurize and heat the powder, the temperature is 100~160℃, the pressure is 560~800MPa, and the holding time is 10~180s;（9）在真空炉内进行烧结，烧结温度为1000~1450℃，烧结保温时间为1~6h；(9) Carry out sintering in a vacuum furnace, the sintering temperature is 1000~1450℃, and the sintering holding time is 1~6h;（10）冷却步骤（9）得到的烧结体即得到该碳纤维增强钛合金复合材料；(10) cooling the sintered body obtained in step (9) to obtain the carbon fiber reinforced titanium alloy composite material;所述钛合金由如下步骤制成：Described titanium alloy is made by following steps:（a）配料：按照Nb：25~32%，Zr：6~8.1%，Sn：11~16.2%，O：0.01~0.18%，RE：1.8~2.6%，Al：3.2~4.2%，余量为Ti进行配料，其中Ti以海绵钛，Zr以海绵锆、Nb采用Ti-52Nb中间合金、Sn采用Ti-68Sn中间合金、RE采用混合稀土、Al采用Ti-Al中间合金，O为上述原料中残留元素；(a) Ingredients: according to Nb: 25~32%, Zr: 6~8.1%, Sn: 11~16.2%, O: 0.01~0.18%, RE: 1.8~2.6%, Al: 3.2~4.2%, the balance Ingredients are made for Ti, among which titanium sponge is used for Ti, zirconium sponge is used for Zr, Ti-52Nb master alloy is used for Nb, Ti-68Sn master alloy is used for Sn, mixed rare earth is used for RE, Ti-Al master alloy is used for Al, and O is among the above raw materials residual elements;（b）熔炼：将步骤（a）配好的料压制成电极，在真空自耗电弧炉中熔炼2次；(b) Smelting: press the material prepared in step (a) into an electrode, and smelt twice in a vacuum consumable electric arc furnace;（c）均匀化退火：均匀化温度为980~1200℃，保持时间为10~18h，退火后进行扒皮去除氧化层；(c) Homogenization annealing: the homogenization temperature is 980~1200℃, the holding time is 10~18h, and the oxide layer is removed by peeling after annealing;（d）锻造：锻造加热温度为920~980℃，保温时间为68~86min，终锻温度为810~860℃；(d) Forging: the forging heating temperature is 920~980°C, the holding time is 68~86min, and the final forging temperature is 810~860°C;（e）热轧：轧制不进行中间退火，轧制道次为8；(e) Hot rolling: rolling without intermediate annealing, and the number of rolling passes is 8;（f）冷轧：冷轧的总变形量为80%；(f) Cold rolling: the total deformation of cold rolling is 80%;（g）固溶热处理：将冷轧板在箱式电阻炉中进行固溶热处理，固溶温度为835-860℃，保温时间为0.8-1.8h，水淬；(g) Solution heat treatment: The cold-rolled sheet is subjected to solution heat treatment in a box-type resistance furnace, the solution temperature is 835-860°C, the holding time is 0.8-1.8h, and water quenching;（h）时效热处理：分为如下四步：时效温度为300~320℃，保温时间为5~18min，水淬；在加热到400~420℃进行第二次时效处理，时效时间为1~1.8h，水淬；再加热到480~495℃进行第三次时效，时效时间为2~2.5h，水淬；再加热到520~550℃进行第四次时效，时效时间为5~8h，水淬；得到钛合金成品。(h) Aging heat treatment: divided into the following four steps: the aging temperature is 300~320°C, the holding time is 5~18min, water quenching; the second aging treatment is carried out after heating to 400~420°C, and the aging time is 1~1.8 h, water quenching; reheating to 480~495°C for the third aging, the aging time is 2~2.5h, water quenching; reheating to 520~550°C for the fourth aging, the aging time is 5~8h, water Quenching; to obtain finished titanium alloy.2.根据权利要求1所述的碳纤维增强钛合金复合材料的制备方法，其特征在于，所述碳纤维去胶处理采用空气灼烧法进行。2. The preparation method of carbon fiber reinforced titanium alloy composite material according to claim 1, characterized in that, the carbon fiber degumming treatment is carried out by an air burning method.3.根据权利要求1或2所述的碳纤维增强钛合金复合材料的制备方法，其特征在于，所述碳纤维中和处理采用KOH或氨水进行中和。3. The method for preparing carbon fiber reinforced titanium alloy composite material according to claim 1 or 2, characterized in that the carbon fiber neutralization treatment is neutralized by KOH or ammonia water.4.根据权利要求1或2所述的碳纤维增强钛合金复合材料的制备方法，其特征在于，所述碳纤维活化处理采用PdCl₂和AgCl为活化液。4. The preparation method of carbon fiber reinforced titanium alloy composite material according to claim 1 or 2, characterized in that, the carbon fiber activation treatment adopts PdCl₂ and AgCl as the activation solution.5.根据权利要求1或2所述的碳纤维增强钛合金复合材料的制备方法，其特征在于，钛合金制备过程中，时效热处理分为如下四步：时效温度为310℃，保温时间为8min，水淬；再加热到420℃进行第二次时效处理，时效时间为1h，水淬；再加热到485℃进行第三次时效，时效时间为2h，水淬；再加热到535℃进行第四次时效，时效时间为5h，水淬。5. The preparation method of carbon fiber reinforced titanium alloy composite material according to claim 1 or 2, characterized in that, in the preparation process of the titanium alloy, the aging heat treatment is divided into the following four steps: the aging temperature is 310°C, the holding time is 8min, Water quenching; reheating to 420°C for the second aging treatment, the aging time is 1h, water quenching; reheating to 485°C for the third aging treatment, the aging time is 2h, water quenching; reheating to 535°C for the fourth Secondary aging, the aging time is 5h, water quenching.6.根据权利要求1或2所述的碳纤维增强钛合金复合材料的制备方法，其特征在于，所述所述钛合金按照重量百分含量由如下成分组成：Nb：28%，Zr：6.8%，Sn：15.2%，O：0.15%，RE：2.1%，Al：3.8%，余量为Ti。6. The method for preparing a carbon fiber reinforced titanium alloy composite material according to claim 1 or 2, wherein the titanium alloy is composed of the following components in terms of weight percentage: Nb: 28%, Zr: 6.8% , Sn: 15.2%, O: 0.15%, RE: 2.1%, Al: 3.8%, and the balance is Ti.7.一种碳纤维增强钛合金复合材料，其特征在于，采用权利要求1~6中任一项的方法制成。7. A carbon fiber reinforced titanium alloy composite material, characterized in that it is made by the method according to any one of claims 1 to 6.