WO2014166364A1 - 一种压电纤维复合物的制备方法 - Google Patents

一种压电纤维复合物的制备方法 Download PDF

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WO2014166364A1
WO2014166364A1 PCT/CN2014/074809 CN2014074809W WO2014166364A1 WO 2014166364 A1 WO2014166364 A1 WO 2014166364A1 CN 2014074809 W CN2014074809 W CN 2014074809W WO 2014166364 A1 WO2014166364 A1 WO 2014166364A1
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piezoelectric ceramic
carbon black
green body
piezoelectric
solvent
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张斗
张野
林秀娟
周科朝
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Central South University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/092—Forming composite materials

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  • the invention relates to a method for preparing a piezoelectric fiber composite.
  • the piezoelectric effect is caused by the existence of asymmetric centers in some crystal structures. Under the action of mechanical stress, the internal positive and negative charge centers will be relatively displaced and polarized, resulting in opposite signs on both ends of the material. The phenomenon of charge is called the positive piezoelectric effect. Conversely, when such materials are subjected to an external electric field, the internal positive and negative charge centers are displaced, resulting in mechanical deformation of the material, called the inverse piezoelectric effect.
  • piezoelectric materials can be used as both a sensor and a driver. It is currently the most widely used type of smart material. Since the 1950s, research on the application of piezoelectric ceramic materials has developed rapidly, such as piezoelectric fuzes, piezoelectric power supplies and other voltage generating devices, as well as vibration accelerometers, fluid monitors and other pressure sensitive sensor components. Development and application. However, for the piezoelectric ceramic block, its hard and brittle characteristics make it impossible to apply to the curved surface, and its large volume and weight also make its application in the intelligent structure greatly limited.
  • NASA Langly Research Center Proposed Piezoelectric Fiber Composites The concept, which consists of piezoelectric ceramic fibers, a polymer matrix and an interdigitated electrode.
  • the composite not only solves the defects of hard and brittle piezoelectric ceramic material, but also has the characteristics of thin thickness, light weight, large bending and torsion, etc., and can be easily attached to various working surfaces including curved surfaces. , greatly expanding the field of its application.
  • piezoelectric fiber composites are widely used in many fields including structural control, shock absorption, energy harvesting and the like.
  • piezoelectric fiber composites such as: W.K Wilkie It is mainly prepared by a thin plate cutting method.
  • a piezoelectric ceramic green body is prepared, and after sintering into a thin plate, equidistant grooves are cut on the surface thereof, and the piezoelectric fiber composite is prepared by a resin encapsulation process.
  • the method can ensure good uniformity between fibers, but the large-sized ceramic thin plate is easily deformed during the sintering process, and the condition control is complicated, and the method has high precision for the cutting equipment, and has large equipment investment and low material utilization rate. Defects such as long production cycle.
  • the above method is difficult to apply to processing piezoelectric fiber composites having fine, uniform fiber spacing, such as less fiber spacing 60 ⁇ m piezoelectric fiber composite.
  • Properly reducing the pitch of the piezoelectric fibers and increasing the content of the piezoelectric phase in the composite is a method to improve the performance of the piezoelectric fiber composite.
  • Zhang Dou A plastic polymer method is proposed, which firstly prepares a green ceramic powder green body and a carbon black green body by a plastic polymer method, and then two kinds of green bodies are arranged in a stack, and the carbon black is sintered to form a pressure.
  • the electric ceramic multilayer structure is formed by filling the structure with a resin, and finally performing the steps of cutting and encapsulating the electrode.
  • the method does not need to rely on high-precision cutting equipment, and the prepared piezoelectric fiber composite fiber has a minimum spacing 5 ⁇ m .
  • this method requires special plastic processing equipment, and the uniformity of the thickness of the green body is difficult to control, and it is necessary to repeatedly process and thin, resulting in high stress and internal structure damage, which tends to cause large fluctuations in product quality and a decrease in the yield.
  • the piezoelectric ceramic green body and the carbon green body prepared by the tape casting process have small internal stress, flexible and controllable thickness, and can directly obtain the piezoelectric ceramic green body and the carbon black green body with the required thickness, thereby obtaining fine and uniform fiber spacing.
  • the composite but the traditional piezoelectric ceramic casting slurry system has problems such as low solid phase content, poor fluidity, and uneven green density, which limits its application.
  • the object of the present invention is to provide a simple process, low equipment requirements, and a product fiber spacing of 3 to 60 ⁇ m. And a method for preparing a piezoelectric fiber composite having stable quality and high yield.
  • Another object of the present invention is to provide an application for optimizing a homogenizing agent for a piezoceramic casting slurry, which can maintain a low viscosity of the slurry while being obtained for casting production while maintaining a high solid phase slurry.
  • the technical solution of the present invention includes:
  • piezoelectric ceramic green body 0.2 to 3.0 ⁇ m piezoelectric ceramic powder, solvent A, dispersant B, plasticizer C , binder D, homogenizing agent E is uniformly mixed to obtain a slurry of piezoelectric ceramics, wherein the weight ratio of solvent A to piezoelectric ceramic powder is (0.25 to 1.50): 1, dispersant B 1 to 5% by weight of the piezoelectric ceramic powder, plasticizer C and binder D are 5 to 10% by weight of the piezoelectric ceramic powder and solvent, respectively, and the homogenizing agent is 5 to 15% by weight of the binder.
  • a piezoelectric ceramic green body having a thickness of 50 to 300 ⁇ m is formed by a casting method, wherein the solvent A is deionized water or absolute ethanol, and the dispersing agent B is one of phosphate ester, corn oil or ammonium polyacrylate.
  • Plasticizer C is phthalate or polyethylene glycol
  • binder D is polyvinyl alcohol or polyvinyl butyral
  • homogenizer E is cyclohexanone
  • binder I is uniformly mixed in proportion, wherein the weight ratio of the solvent F to the carbon black is (2 to 4): 1, the dispersant G is 1 to 3% by weight of the carbon black, the plasticizer H and the binder I Both carbon black and solvent weight 5 to 10%, cast carbon black body 10 ⁇ 100 ⁇ m, wherein solvent F is anhydrous ethanol, dispersant G is byk-163, plasticizer H For phthalate or polyethylene glycol, binder I is polyvinyl butyral;
  • the laminated green body prepared by the step c is heated to a rate of 0.5 to 5 ° C /min to 450 ⁇ 600 °C, then increase the temperature to 1200 ⁇ 1280 °C at 6 ⁇ 10 °C / min, keep warm 0.5 ⁇ 4 After an hour, the furnace is cooled to obtain a piezoelectric ceramic multilayer structure;
  • the interdigitated electrode includes an electrode and a flexible substrate, the electrode is prepared on a flexible substrate, the electrode includes a positive electrode and a negative electrode, and the positive and negative fingers are staggered.
  • Another object of the invention is achieved by using cyclohexanone as The homogenizing agent is added to the slurry of the piezoelectric ceramic so that the piezoelectric ceramic slurry can maintain the low viscosity of the slurry and be used for casting production while obtaining a high solid phase slurry.
  • the high solid content slurry is obtained while maintaining the low viscosity of the slurry, making it suitable for casting production, and at the same time improving
  • the density uniformity of the piezoelectric ceramic green body effectively controls the high shrinkage rate and large deformation amount generated during the sintering process of the casting system, and the preparation process is simple and reliable, and does not need to rely on special equipment.
  • the thickness of the method can be 10 to 100 m m by the method of the invention.
  • the uniform and controllable carbon black green body enables the laminated structure green body to be subjected to subsequent pressurization and thinning, reduces the stress in the green body, and avoids the destruction of the internal structure of the green body, and at the same time, the carbon black green body is sintered without Impurities remain. Therefore, the method can obtain a piezoelectric ceramic fiber composite having a uniform, fine fiber pitch.
  • Figure 1 a is a-c according to the invention Piezoelectric fiber composite green body prepared by the method of step, carbon black sacrificial film in dark region, piezoelectric fiber green body in bright color region;
  • FIG. 1b is a-d according to the invention The resin-packed piezoelectric fiber composite obtained by the method of the step, the bright color region is a piezoelectric fiber, and the dark region is a resin matrix.
  • the fiber pitch is about 10 ⁇ m;
  • FIG. 1c is a-d according to the present invention.
  • the method of step is to obtain a piezoelectric fiber composite after resin encapsulation, wherein the bright color region is a piezoelectric fiber, and the dark region is a resin matrix.
  • the fiber pitch is about 5 ⁇ m;
  • FIG. 1d is a-e according to the present invention.
  • the micro-morphology of the piezoelectric fiber obtained by the step method has no voids between the crystal grains, indicating that the sintering density is high.
  • Figure 2 shows the effect of cyclohexanone on the viscosity of the slurry.
  • the polyline before optimization is uncyclohexanone
  • the solid content of the slurry reaches 70%.
  • the viscosity exceeds 0.5 Pa s and the casting operation cannot be performed.
  • the viscosity is much lower than 0.5 Pa s after the solid content of the slurry reaches 70%. , the casting operation can still be carried out smoothly.
  • Figure 3 shows the PZT of Comparative Example 1.
  • the fiber microstructure diagram there are many gaps between the grains, indicating that the fiber cannot be densified due to the low solid phase content of the slurry.
  • Figure 4 shows the sintered PZT of Comparative Example 2 Piezoelectric ceramic sheets can be seen to be structurally curved and cannot be used for the preparation of piezoelectric fiber composites.
  • This example is a method for preparing a piezoelectric fiber composite in which a PZT piezoelectric fiber and an epoxy resin matrix are combined, and has the following steps:
  • the absolute ethanol and the carbon black powder with a particle size of 25 nm are mixed at a weight ratio of 4:1, and then added to the weight of the carbon black powder by 1%.
  • Byk-163 is a dispersant, mixed into a primary slurry, and then added to the primary slurry in the absolute ethanol and carbon black powder weight 5%
  • Diethyl phthalate is a plasticizer, and the binder is polyvinyl butyral equivalent to 5% by weight of anhydrous ethanol and carbon black powder in the primary slurry, and 10 ⁇ m carbon black is produced by casting method.
  • Billet is a dispersant, mixed into a primary slurry, and then added to the primary slurry in the absolute ethanol and carbon black powder weight 5%
  • Diethyl phthalate is a plasticizer
  • the binder is polyvinyl butyral equivalent to 5% by weight of anhydrous ethanol and carbon black powder in the primary slurry, and 10 ⁇ m carbon black is produced by casting method
  • the carbon black green body prepared with step b and a The piezoelectric ceramic green body prepared by the step is cut according to the required length and width, and is stacked and closely spaced to each other to form a carbon black having a lamellar structure/ Piezoelectric ceramic laminated green body, and then dried to deionized water and anhydrous ethanol to volatilize completely;
  • the laminated green body is heated to 450 °C at a rate of 0.5 °C / min, and then heated to a rate of 6 °C / min to After 1200 °C, after 4 hours of heat preservation, the furnace is cooled to obtain a piezoelectric ceramic multilayer structure;
  • This embodiment is suitable for preparing piezoelectric fiber composites having a fiber pitch of 3 ⁇ m;
  • This example is a method for preparing a piezoelectric fiber composite in which a PZT piezoelectric fiber and an epoxy resin matrix are combined, and has the following steps:
  • the absolute ethanol and the PZT powder with a particle size of 3 ⁇ m are mixed at a weight ratio of 0.25:1, and then the equivalent of PZT is added.
  • the weight of powder 5% of triethyl phosphate is a dispersing agent, and the mixture is uniformly mixed into a primary slurry, and then added to the primary slurry corresponding to 10% by weight of PZT powder and absolute ethanol.
  • the polyethylene glycol is a plasticizer, and the binder is polyvinyl butyral equivalent to 10% by weight of the PZT powder and the absolute ethanol in the primary slurry, and the homogenizing agent is 15% by weight of the binder.
  • Ketone made by casting 300 ⁇ m green body;
  • the absolute ethanol and 250nm carbon black powder are mixed at a weight ratio of 2.3:1, and then added to the weight of the carbon black powder by 3%.
  • Byk-163 is a dispersant, mixed into a primary slurry, and then added to the primary slurry in the absolute ethanol and carbon black powder weight 10%
  • the polyethylene glycol is a plasticizer, and the binder is polyvinyl butyral corresponding to 10% by weight of anhydrous ethanol and carbon black powder in the primary slurry, and a carbon black green body of 100 ⁇ m is formed by casting;
  • the carbon black green body prepared with step b and a The piezoelectric ceramic green body prepared by the step is cut according to the required length and width, and is stacked and closely spaced to each other to form a carbon black having a lamellar structure/ Piezoelectric ceramic laminated green body, and then dried until anhydrous ethanol is completely evaporated;
  • the laminated green body is heated to 600 °C at a rate of 5 °C / min and then heated to a rate of 10 °C /min to After 1280 °C, after 0.5 h of heat preservation, the piezoelectric ceramic multilayer structure is obtained after cooling with the furnace;
  • This embodiment is suitable for preparing a piezoelectric fiber composite having a fiber pitch of 60 ⁇ m;
  • This example is a method for preparing a piezoelectric fiber composite in which a PNN-PZT piezoelectric fiber and an epoxy resin matrix are combined, and has the following steps:
  • the absolute ethanol and the carbon black powder with a particle size of 100 nm are mixed at a weight ratio of 4:1, and then added to the weight of the carbon black powder by 3%.
  • Byk-163 is a dispersant, mixed into a primary slurry, and then added to the primary slurry in the absolute ethanol and carbon black powder weight 8%
  • Tributyl phthalate is a plasticizer, and the binder is polyvinyl butyral equivalent to 8% by weight of the primary slurry anhydrous ethanol and carbon black powder, and 80 ⁇ m carbon black green body is formed by casting method. ;
  • the carbon black green body prepared with step b and a The piezoelectric ceramic green body prepared in the step is cut into several pieces according to the required size, and is stacked and closely spaced to each other, and the carbon black/piezoceramic laminated green body having a lamellar structure is dried, and the solvent is completely evaporated. ;
  • the laminated green body is heated to 500 °C at a rate of 3 °C /min and then heated to a rate of 8 °C /min to After 1250 °C, after 2 hours of heat preservation, the furnace is cooled to obtain a piezoelectric ceramic multilayer structure;
  • This embodiment is suitable for preparing piezoelectric fiber composites having a fiber pitch of 20 ⁇ m;
  • a method for preparing a piezoelectric fiber composite compounded by a PMN-PT piezoelectric fiber and an epoxy resin matrix has the following steps:
  • the carbon black green body prepared with step b and a The piezoelectric ceramic green body prepared by the step is cut according to the required length and width, and is stacked and closely spaced to each other to form a carbon black having a lamellar structure/ Piezoelectric ceramic laminated green body, and then dried until anhydrous ethanol is completely evaporated;
  • the laminated green body is heated to 600 °C at a rate of 5 °C / min and then heated to a rate of 10 °C /min to After 1280 °C, after 0.5 h of heat preservation, the piezoelectric ceramic multilayer structure is obtained after cooling with the furnace;
  • This example is suitable for the preparation of piezoelectric fiber composites having a fiber pitch of 40 ⁇ m.
  • Example 2 The raw materials and operation steps of Example 2 were used, but a.
  • the homogenizer cyclohexanone was not added or added in the step, and the other conditions were unchanged.
  • the corresponding solid content was adjusted to obtain the viscosity line before optimization and after optimization.
  • the viscosity of the obtained PZT slurry is shown in Figure 2.
  • Optimize the third point of the front fold line ie, the last point value
  • the viscosity of the slurry of the resulting PZT slurry with the homogenizer cyclohexanone is significantly higher than that of the third point of the optimized fold line in Figure 2. More than 0.5 Pa At the highest value of s, the slurry will stick to the knife edge, making it impossible to perform the casting operation.
  • Example 2 In the same manner as in Example 2, a. Anhydrous ethanol and PZT powder having a particle size of 3 ⁇ m were mixed at a weight ratio of 2:1. Income See Figure 3 for the PZT fiber microstructure. There are many gaps between the grains, which indicates that there are many voids between the grains due to the low solid content of the slurry, indicating that the fibers cannot be densified due to the low solid content of the slurry.
  • Example 2 In the same manner as in Example 2, b, anhydrous ethanol and 250 nm of carbon black powder were mixed at a weight ratio of 1:1.
  • the resulting sintered See Figure 4 for the PZT piezoelectric ceramic sheet. It can be seen that the structure is curved, which indicates that the PZT sheet is bent after sintering due to the mismatch between the PZT green body and the carbon black green body. Cannot be used in the preparation of piezoelectric fiber composites.

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Abstract

一种压电纤维复合物的制备方法，包括以下步骤：a.制备压电陶瓷生坯；b.制备炭黑生坯；c.将b步骤制备的炭黑生坯和a步骤制备并剥离的压电陶瓷生坯切割，并相互间隔堆叠成具有层片状结构的炭黑/压电陶瓷叠层生坯，再干燥；d.将由c步骤制备的叠层生坯以0.5〜5°C/min的速率升温至450〜600°C，再以6〜10°C/min的速率升温至1200〜1280°C，保温0.5〜4小时后，随炉冷却，得到压电陶瓷多层结构；e.将得到的压电陶瓷多层结构填充环氧树脂，于25〜60°C下固化10〜24小时后，切割成所需要的尺寸，再使用叉指状电极进行包封，得到压电纤维复合物。该方法优化了传统压电陶瓷流延浆料体系，提高了压电陶瓷生坯的密度均匀性，有效地控制了流延体系烧结过程中产生的高收缩率和大变形量问题。

Description

一种压电纤维复合物的制备方法
技术领域
本发明涉及一种压电纤维复合物的制备方法。
背景技术
压电效应是由于某些材料在晶体结构上存在不对称中心而造成的，在机械应力作用下，内部正负电荷中心将产生相对位移而发生极化，导致材料两端表面出现符号相反的束缚电荷的现象，称为正压电效应。反之，当这类材料在外电场作用下，其内部正负电荷中心产生移位，导致材料发生机械变形，称为逆压电效应。
利用压电效应，压电材料既可以用传感器，又可以用作驱动器 , 是目前应用最广泛的一类智能材料。自上世纪五十年代以来，关于压电陶瓷材料应用的研究发展很快，如压电引信、压电电源等多种电压发生器件以及振动加速度计、流体监控器等多种压敏传感器件的开发与应用。然而，对于压电陶瓷块体而言，其硬而脆的特性使其不能应用于曲面，较大的体积和重量也使其在智能结构中的应用受到很大的局限。
为了解决块体材料的应用局限性， NASA Langly Research Center 提出压电纤维复合物（ Macro Fiber Composites ）的概念，它是由压电陶瓷纤维，聚合物基体和叉指状电极所组成。该复合物不仅解决了压电陶瓷块体材料硬而脆等缺陷，同时还具有厚度薄，重量轻，可进行大幅弯曲和扭转等特点，很容易粘贴到包括曲面在内的多种工作表面上，极大地拓展了其应用的领域。目前，压电纤维复合物被广泛的应用于包括结构控制、减震、能量采集等诸多领域。
目前关于压电纤维复合物制备方面的报道，如： W.K Wilkie 等主要采用薄板切割法制备，其首先制备压电陶瓷生坯，烧结成薄板后在其表面切割出等距凹槽，再通过树脂包封等工序制备压电纤维复合物。该方法可以保证纤维间良好的均匀性，但是大尺寸陶瓷薄板在烧结过程中极易变形，条件控制复杂，并且该方法对于切割设备的精度要求很高，且存在设备投资大、材料利用率低、生产周期长等缺陷。此外，上述方法很难适用于加工具有精细、均匀纤维间距的压电纤维复合物，如纤维间距小于 60µm 的压电纤维复合物。适当的减小压电纤维间距，提高压电相在复合物中的含量是提高压电纤维复合物性能的一种方法， Zhang Dou 等人提出了一种塑性聚合物法，其首先采用塑性聚合物法制备含有压电陶瓷粉末生坯和炭黑生坯，然后将两种生坯间隔排列叠压，烧结去除炭黑，形成压电陶瓷多层结构，将该结构填充树脂后固化，最后进行切割、包封电极等步骤。该方法不需要依赖高精密的切割设备，制备出的压电纤维复合物纤维间距最小可达 5µm 。但该方法需要专用的塑性加工设备，而且生坯厚度的均匀性控制困难，且需要反复加工减薄，带来高的应力和内部结构的损坏，容易造成产品质量波动较大，合格率下降。采用流延成型工艺制备压电陶瓷生坯和炭生坯内部应力小，厚度灵活可控，可直接获得所需厚度的压电陶瓷生坯和炭黑生坯，从而得到具有精细，均匀纤维间距的复合物，但传统的压电陶瓷流延浆料体系存在固相含量低，流动性差，生坯密度不均匀等问题，限制了其应用。
发明内容
本发明的目的是提供一种工艺简单，对设备要求低，产品纤维间距为 3 ～ 60µm 并且质量稳定，合格率高的压电纤维复合物的制备方法。
本发明的另一目的在于提供一种优化压电陶瓷流延浆料的均匀化剂的应用，在获得高固相浆料的同时，仍可保持浆料的低粘度并适用于流延生产。
为了达到上述目的，本发明的技术方案包括：
a. 制备压电陶瓷生坯：将 0.2 ～ 3.0µm 的压电陶瓷粉末、溶剂 A 、分散剂 B 、增塑剂 C 、粘结剂 D 、均匀化剂 E 按比例混合均匀得到压电陶瓷的浆料，其中溶剂 A 与压电陶瓷粉末的重量比为（ 0.25 ～ 1.50 ） :1 、分散剂 B 为压电陶瓷粉末重量的 1 ～ 5% 、增塑剂 C 和粘结剂 D 分别为压电陶瓷粉末和溶剂重量的 5 ～ 10% 、均匀化剂为粘结剂重量的 5 ～ 15% ，再用流延法制成厚度为 50 ～ 300µm 的压电陶瓷生坯，其中溶剂 A 为去离子水或无水乙醇，分散剂 B 为磷酸盐酯、玉米油或聚丙烯酸铵中的一种，增塑剂 C 为邻苯二甲酸酯或聚乙二醇，粘结剂 D 为聚乙烯醇或聚乙烯醇缩丁醛，均匀化剂 E 为环己酮；
b. 制备炭黑生坯：将粒度为 20 ～ 350nm 炭黑粉末，溶剂 F ，分散剂 G ，增塑剂 H ，粘结剂 I 按比例混合均匀，其中溶剂 F 与炭黑的重量比为（ 2 ～ 4 ） :1 、分散剂 G 为炭黑重量的 1 ～ 3% 、增塑剂 H 和粘结剂 I 均为炭黑和溶剂重量的 5 ～ 10% ，用流延法制成 10 ～ 100µm 的炭黑生坯，其中溶剂 F 为无水乙醇，分散剂 G 为 byk-163 ，增塑剂 H 为邻苯二甲酸酯或聚乙二醇，粘结剂 I 为聚乙烯醇缩丁醛；
c. 将 b 步骤制备的炭黑生坯和 a 步骤制备并剥离的压电陶瓷生坯按照所需长度和宽度的尺寸切割，并将其相互间隔堆叠成紧密结合，具有层片状结构的炭黑 / 压电陶瓷叠层生坯，再干燥至溶剂 A 和溶剂 F 挥发完全；
d. 根据压电陶瓷粉末含量，将由 c 步骤制备的叠层生坯以 0.5 ～ 5 ℃ /min 的速率升温至 450 ～ 600 ℃ ，再以 6 ～ 10 ℃ /min 的速率升温至 1200 ～ 1280 ℃ ，保温 0.5 ～ 4 小时后，随炉冷却，得到压电陶瓷多层结构；
e. 将得到的压电陶瓷多层结构填充环氧树脂，于 25 ～ 60 ℃ 下固化 10 ～ 24 小时后，切割成所需要的尺寸，再使用叉指状电极进行包封，得到压电纤维复合物。
作为改进，所述叉指状电极包括电极和柔性基板，电极制备在柔性基板上，电极包含正极和负极，并且正极指部和负极指部交错排列。
本发明的另一目的的实现在于，将环已酮作为 的均匀化剂添加到压电陶瓷的浆料中，使得压电陶瓷浆料在获得高固相浆料的同时，仍可保持浆料的低粘度并用于流延生产。
有益效果：
1. 通过加入均匀化剂环己酮来优化传统压电陶瓷流延浆料体系，在获得高固相含量浆料的同时，保持了浆料的低粘度，使其适用于流延生产，同时提高了压电陶瓷生坯的密度均匀性，有效地控制了流延体系烧结过程中产生的高收缩率和大变形量问题，且制备工艺简单可靠，不需要依赖专用设备。
2. 采用本发明方法可制得厚度为 10 ～ 100 m m 且均匀可控的炭黑生坯，使叠层结构生坯不需要后续加压减薄，减小了生坯中的应力，避免了生坯内部结构的破坏，同时炭黑生坯烧结后无杂质残留。因此，该方法可获得具有均匀，精细纤维间距的压电陶瓷纤维复合物。
附图说明
图 1 a 为按本发明 a-c 步的方法制得的压电纤维复合物生坯，暗色区域位炭黑牺牲膜，亮色区域位压电纤维生坯；图 1b 为按本发明 a- d 步的方法制得的树脂封装后的压电纤维复合物，亮色区域为压电纤维，暗色区域为树脂基体，由图可知，纤维间距约为 10 μ m ；图 1c 为按本发明 a- d 步的方法制得树脂封装后的压电纤维复合物，亮色区域为压电纤维，暗色区域为树脂基体，由图可知，纤维间距约为 5 μ m ；图 1d 为按本发明 a- e 步的方法制得的压电纤维的微观形貌 , 晶粒之间无空隙，表明烧结致密度高。
图 2 为环己酮对浆料粘度的影响，其中优化前的折线为未加环已酮时，在浆料固相含量达到 70% 后，粘度超过 0.5 Pa s ，无法进行流延操作；而优化前的折线为加环已酮后，在浆料固相含量达到 70% 后粘度远低于 0.5 Pa s ，仍可顺利的进行流延操作。
图 3 为对比例 1 的 PZT 纤维显微结构图，晶粒之间有很多空隙，表明由于浆料固相含量低，纤维无法致密化。
图 4 为对比例 2 的 烧结后的 PZT 压电陶瓷片层，可见其结构弯曲，无法用于压电纤维复合物的制备。
具体实施方式
实施例 1
本实例为 PZT 压电纤维与环氧树脂基体复合的压电纤维复合物的制备方法，有如下步骤：
a. 首先将去离子水与粒度为 0.2µm 的 PZT 粉末按 1.5:1 的重量比混合，再加入相当于 PZT 粉末重量 1% 的聚丙烯酸铵为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中 PZT 粉末和去离子水重量 5% 的邻苯二甲酸二乙酯为增塑剂，粘结剂为相当于初级浆料中 PZT 粉末和去离子水重量 5% 的聚乙烯醇，均匀化剂为粘结剂重量 5% 的环己酮，用流延法制成 50µm 的生坯；
b. 首先将无水乙醇和粒度为 25nm 的炭黑粉末按重量比 4:1 混合，再加入相当于炭黑粉末重量 1% 的 byk-163 为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中无水乙醇和炭黑粉末重量 5% 邻苯二甲酸二乙酯为增塑剂，粘结剂为相当于初级浆料中无水乙醇和炭黑粉末重量 5% 的聚乙烯醇缩丁醛，用流延法制成 10µm 的炭黑生坯；
c. 将用 b 步骤制备的炭黑生坯和用 a 步骤制备的压电陶瓷生坯按照所需长度和宽度的尺寸切割，并将其相互间隔堆叠成紧密结合，具有层片状结构的炭黑 / 压电陶瓷叠层生坯，再干燥至去离子水和无水乙醇挥发完全；
d. 将叠层生坯以 0.5 ℃ /min 的速率升温至 450 ℃ ，再以 6 ℃ /min 的速率升温至 1200 ℃ ，保温 4h 后，随炉冷却，得到压电陶瓷多层结构；
e. 将得到的压电陶瓷多层结构填充环氧树脂，于 25 ℃ 下固化 24h 后，切割成所需要的尺寸，再包封叉指状电极，得到压电纤维复合物。
本实施例适用于制备纤维间距为 3µm 的压电纤维复合物；
实施例 2
本实例为 PZT 压电纤维与环氧树脂基体复合的压电纤维复合物的制备方法，有如下步骤：
a. 首先将无水乙醇和粒度为 3µm 的 PZT 粉末按重量比 0.25:1 混合，再加入相当于 PZT 粉末重量 5% 的磷酸三乙酯为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中 PZT 粉末和无水乙醇重量 10% 的聚乙二醇为增塑剂，粘结剂为相当于初级浆料中 PZT 粉末和无水乙醇重量 10% 的聚乙烯醇缩丁醛，均匀化剂为粘结剂重量 15% 的环己酮，用流延法制成 300µm 的生坯；
b. 首先将无水乙醇和 250nm 的炭黑粉末按重量比 2.3:1 混合，再加入相当于炭黑粉末重量 3% 的 byk-163 为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中无水乙醇和炭黑粉末重量 10% 的聚乙二醇为增塑剂，粘结剂为相当于初级浆料中无水乙醇和炭黑粉末重量 10% 的聚乙烯醇缩丁醛，用流延法制成 100µm 的炭黑生坯；
c. 将用 b 步骤制备的炭黑生坯和用 a 步骤制备的压电陶瓷生坯按照所需长度和宽度的尺寸切割，并将其相互间隔堆叠成紧密结合，具有层片状结构的炭黑 / 压电陶瓷叠层生坯，再干燥至无水乙醇挥发完全；
d. 将叠层生坯以 5 ℃ /min 的速率升温至 600 ℃ ，再以 10 ℃ /min 的速率升温至 1280 ℃ ，保温 0.5h 后，随炉冷却，得到压电陶瓷多层结构；
e. 将得到的压电陶瓷多层结构填充环氧树脂，于 40 ℃ 下固化 15h 后，切割成所需要的尺寸，再包封叉指状电极，得到压电纤维复合物。
本实施例适用于制备纤维间距为 60µm 的压电纤维复合物；
实施例 3
本实例为 PNN-PZT 压电纤维与环氧树脂基体复合的压电纤维复合物的制备方法，有如下步骤：
a. 首先将无水乙醇和粒度为 1.5µm 的 PNN-PZT 粉末按重量比 0.67:1 混合，再加入相当于 PNN-PZT 粉末重量 3% 的玉米油为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中 PNN-PZT 粉末和无水乙醇重量 8% 的由邻苯二甲酸三丁酯为增塑剂，粘结剂为相当于初级浆料中 PNN-PZT 粉末和无水乙醇重量 8% 的聚乙烯醇缩丁醛，均匀化剂为粘结剂重量 ,10% 的环己酮，用流延法制成 200µm 的生坯；
b. 首先将无水乙醇和粒度为 100nm 的炭黑粉末按重量比 4:1 混合，再加入相当于炭黑粉末重量 3% 的 byk-163 为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中无水乙醇和炭黑粉末重量 8% 邻苯二甲酸三丁酯为增塑剂，粘结剂为相当于初级浆料无水乙醇和炭黑粉末重量 8% 的聚乙烯醇缩丁醛，用流延法制成 80µm 的炭黑生坯；
c. 将用 b 步骤制备的炭黑生坯和用 a 步骤制备的压电陶瓷生坯按照所需尺寸切割成若干块，并将其相互间隔堆叠成紧密结合，具有层片状结构的炭黑 / 压电陶瓷叠层生坯，再干燥至溶剂挥发完全；
d. 将叠层生坯以 3 ℃ /min 的速率升温至 500 ℃ ，再以 8 ℃ /min 的速率升温至 1250 ℃ ，保温 2h 后，随炉冷却，得到压电陶瓷多层结构；
e. 将得到的压电陶瓷多层结构填充环氧树脂，于 60 ℃ 下固化 10h 后，切割成所需要的尺寸，再包封叉指状电极，得到压电纤维复合物。
本实施例适用于制备纤维间距为 20µm 的压电纤维复合物；
实施例 4
本实施例为 PMN-PT 压电纤维与环氧树脂基体复合的压电纤维复合物的制备方法，有如下步骤：
a. 首先将无水乙醇和粒度为 1.5µm 的 PMN-PT 粉末按重量比 0.25:1 混合，再加入相当于 PZT 粉末重量 5% 的玉米油为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中 PMN-PT 和无水乙醇重量 10% 的聚乙二醇为增塑剂，粘结剂为相当于初级浆料中 PMN-PT 和无水乙醇重量 10% 的聚乙烯醇缩丁醛，均匀化剂为粘结剂重 ,15% 的环己酮，用流延法制成 300µm 的生坯；
b. 首先将无水乙醇和 100nm 的炭黑粉末按重量比 2.3:1 混合，再加入相当于炭黑粉末重量 3% 的 byk-163 为分散剂，混合均匀成初级浆料，然后加入相当于初级浆料中无水乙醇和炭黑粉末重量 10% 的聚乙二醇为增塑剂，粘结剂为相当于初级浆料中无水乙醇和炭黑粉末重量 10% 的聚乙烯醇缩丁醛，用流延法制成 80µm 的炭黑生坯；
c. 将用 b 步骤制备的炭黑生坯和用 a 步骤制备的压电陶瓷生坯按照所需长度和宽度的尺寸切割，并将其相互间隔堆叠成紧密结合，具有层片状结构的炭黑 / 压电陶瓷叠层生坯，再干燥至无水乙醇挥发完全；
d. 将叠层生坯以 5 ℃ /min 的速率升温至 600 ℃ ，再以 10 ℃ /min 的速率升温至 1280 ℃ ，保温 0.5h 后，随炉冷却，得到压电陶瓷多层结构；
e. 将得到的压电陶瓷多层结构填充环氧树脂，于 40 ℃ 下固化 15h 后，切割成所需要的尺寸，再包封叉指状电极，得到压电纤维复合物。
本实例适用于制备纤维间距为 40µm 的压电纤维复合物。
对比例 1
采用的是实施例 2 原料及操作步骤，，但 a. 步中分别不加入或加入均匀化剂环己酮，其它条件不变，调整相应的固含量得到优化前和优化后的粘度折线。所得的 PZT 浆料的粘度参见图 2 优化前折线第三点（即最后一个点值）；与采用均匀化剂环己酮的所得的 PZT 浆料的浆料的粘度参见图 2 优化后的折线第三点相比，粘度显著上升，超过 0.5 Pa s 的最高值，浆料将与刀口粘连，从而无法进行流延操作。
对比例 2
其它同实施例 2 ， a. 步中无水乙醇和粒度为 3µm 的 PZT 粉末按重量比 2:1 混合。所得的 PZT 纤维显微结构图参见图 3 ，晶粒之间有很多空隙，表明由于浆料固相含量低，晶粒之间有很多空隙，表明由于浆料固相含量低，纤维无法致密化。
对比例 3
其它同实施例 2 ， b 步中无水乙醇和 250nm 的炭黑粉末按重量比 1:1 混合。所得的烧结后的 PZT 压电陶瓷片层参见图 4 ，可见其结构弯曲，表明由于 PZT 生坯与炭黑生坯烧结收缩不匹配，导致烧结后 PZT 片层弯曲， 无法用于压电纤维复合物的制备。

Claims (3)

1. 一种压电纤维复合物的制备方法，其特征是包括：
a. 制备压电陶瓷生坯：将 0.2 ～ 3.0μm 的压电陶瓷粉末、溶剂 A 、分散剂 B 、增塑剂 C 、粘结剂 D 、均匀化剂 E 按比例混合均匀，其中溶剂 A 与压电陶瓷粉末的重量比为（ 0.25 ～ 1.50 ） :1 、分散剂 B 为压电陶瓷粉末重量的 1 ～ 5% 、增塑剂 C 和粘结剂 D 分别为压电陶瓷粉末和溶剂 A 重量的 5 ～ 10% 、均匀化剂 E 为粘结剂 D 重量的 5 ～ 15% ，再用流延法制成厚度为 50 ～ 300μm 的生坯，其中溶剂 A 为去离子水或无水乙醇，分散剂 B 为磷酸盐酯、玉米油或聚丙烯酸铵中的一种，增塑剂 C 为邻苯二甲酸酯或聚乙二醇，粘结剂 D 为聚乙烯醇或聚乙烯醇缩丁醛，均匀化剂 E 为环己酮；
b. 制备炭黑生坯：将粒度为 20 ～ 350nm 炭黑粉末，溶剂 F ，分散剂 G ，增塑剂 H ，粘结剂 I 按比例混合均匀，其中溶剂 F 与炭黑的重量比为（ 2 ～ 4 ） :1 、分散剂 G 为炭黑重量的 1 ～ 3% 、增塑剂 H 和粘结剂 I 均为炭黑和溶剂 F 重量的 5 ～ 10% ，用流延法制成 10 ～ 100μm 的炭黑生坯，其中溶剂 F 为无水乙醇，分散剂 G 为 byk-163 ，增塑剂 H 为邻苯二甲酸酯或聚乙二醇，粘结剂 I 为聚乙烯醇缩丁醛；
c. 将 b 步骤制备的炭黑生坯和 a 步骤制备并剥离的压电陶瓷生坯按照所需长度和宽度的尺寸切割，并将其相互间隔堆叠成紧密结合，具有层片状结构的炭黑 / 压电陶瓷叠层生坯，再干燥至溶剂 A 和溶剂 F 挥发完全；
d. 将由 c 步骤制备的叠层生坯以 0.5 ～ 5 ℃ /min 的速率升温至 450 ～ 600 ℃ ，再以 6 ～ 10 ℃ /min 的速率升温至 1200 ～ 1280 ℃ ，保温 0.5 ～ 4 小时后，随炉冷却，得到压电陶瓷多层结构；
e. 将得到的压电陶瓷多层结构填充环氧树脂，于 25 ～ 60 ℃ 下固化 10 ～ 24 小时后，切割成所需要的尺寸，再使用叉指状电极进行包封，得到压电纤维复合物。
2. 根据权利要求 1 的一种压电纤维复合物的制备方法，其特征在于，所述叉指状电极包括电极和柔性基板，电极制备在柔性基板上，电极包含正极和负极，并且正极指部和负极指部交错排列。
3 . 一种均匀化剂在制备 压电陶瓷生坯浆料中的应用，其特征在于，将环已酮作为的均匀化剂添加到压电陶瓷生坯的浆料中，使得压电陶瓷生坯浆料在获得高固相浆料的同时，仍可保持浆料的低粘度并用于流延生产。
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