CN116394600A - Siloxane modified phthalonitrile resin matrix composite material and preparation method thereof - Google Patents
Siloxane modified phthalonitrile resin matrix composite material and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于复合材料技术领域，具体涉及一种硅氧烷改性邻苯二甲腈树脂基复合材料及其制备方法。The invention belongs to the technical field of composite materials, and in particular relates to a siloxane-modified phthalonitrile resin-based composite material and a preparation method thereof.
背景技术Background technique
邻苯二甲腈树脂是一类具有高性能的热固性树脂，其分子结构中氰基由于可以通过热加成聚合反应在树脂体系中形成N杂环结构，因此赋予了邻苯二甲腈树脂优异的热稳定性、化学稳定性、低吸水性和优异的介电性能等。邻苯二甲腈树脂及其复合材料具有优异的综合性能，因此被广泛应用于航空航天、船舶等尖端技术领域。Phthalonitrile resin is a kind of thermosetting resin with high performance. The cyano group in its molecular structure can form N heterocyclic structure in the resin system through thermal addition polymerization, so it endows phthalonitrile resin with excellent performance. Excellent thermal stability, chemical stability, low water absorption and excellent dielectric properties. Phthalonitrile resin and its composite materials have excellent comprehensive properties, so they are widely used in cutting-edge technical fields such as aerospace and ships.
邻苯二甲腈树脂基复合材料的成型，目前通常采用低沸点有机溶剂(如乙醚、丙酮)将邻苯二甲腈树脂溶解之后，再涂覆于纤维布上，之后进行热压固化，如专利CN108454135A《一种邻苯二甲腈树脂预浸料、复合材料及其制备方法》。该方法中使用低沸点溶剂用料较大，100质量份的邻苯二甲腈树脂需使用100-185质量份低沸点溶剂，在实际制备过程中，会造成有毒有机溶剂的大量挥发，不利于现场施工人员身体健康和环保需求。此外，过量的有机溶剂残留会造成复合材料在制备过程中孔隙率增高，导致最终制备复合材料力学性能下降。另外一种邻苯二甲腈树脂基复合材料的成型方法是通过控制热压成型工艺，使邻苯二甲腈树脂熔融后浸润纤维布，然后继续加温加压固化成型，如专利CN113211828B《一种邻苯二甲腈树脂碳纤维布复合材料及其制备方法》。该方法制备工艺复杂，需要将邻苯二甲腈树脂与固化剂先破碎成粉混合均匀后，在180-190℃熔融浸润纤维布，随后通过梯度热压固化成型，工艺较为复杂。The molding of phthalonitrile resin-based composite material usually adopts low-boiling point organic solvents (such as ether, acetone) to dissolve phthalonitrile resin at present, and then coats it on the fiber cloth, and then carries out thermocompression curing, such as Patent CN108454135A "A phthalonitrile resin prepreg, composite material and preparation method thereof". In this method, the use of low-boiling point solvent materials is relatively large, and 100-185 mass parts of phthalonitrile resins need to use 100-185 mass parts of low-boiling point solvents. In the actual preparation process, it will cause a large amount of volatilization of toxic organic solvents, which is not conducive to On-site construction personnel's physical health and environmental protection needs. In addition, excessive organic solvent residues will increase the porosity of the composite material during the preparation process, resulting in a decrease in the mechanical properties of the final composite material. Another molding method of phthalonitrile resin-based composite material is to make the phthalonitrile resin melt and impregnate the fiber cloth by controlling the hot-press molding process, and then continue to heat and pressurize and solidify the molding, such as patent CN113211828B "a A kind of phthalonitrile resin carbon fiber cloth composite material and its preparation method. The preparation process of this method is complicated, and the phthalonitrile resin and the curing agent need to be crushed into powder and mixed evenly, then melted and infiltrated into the fiber cloth at 180-190° C., and then solidified and formed by gradient hot pressing. The process is relatively complicated.
发明内容Contents of the invention
本发明的目的是为了解决现有邻苯二甲腈树脂基复合材料力学性能差、制备工艺复杂等问题，提供一种硅氧烷改性邻苯二甲腈树脂基复合材料及其制备方法，将“-Si-O-”结构引入邻苯二甲腈化合物中，在具有邻苯二甲腈结构的同时，兼具硅氧烷结构，使以该化合物为单体的树脂兼具硅氧烷和邻苯二甲腈树脂两者聚合物基体的优势，所得硅氧烷改性邻苯二甲腈树脂单体玻璃化转变温度降低至-12～-35.6℃。所得液态邻苯二甲腈树脂单体可以不使用有机溶剂溶解，在室温下直接涂覆在纤维布上制备邻苯二甲腈树脂基复合材料预浸料。The purpose of the present invention is to provide a siloxane-modified phthalonitrile resin-based composite material and a preparation method thereof in order to solve the problems of poor mechanical properties and complex preparation process of the existing phthalonitrile resin-based composite materials, The "-Si-O-" structure is introduced into the phthalonitrile compound, which not only has the phthalonitrile structure, but also has a siloxane structure, so that the resin with this compound as a monomer also has a siloxane structure. The glass transition temperature of the obtained siloxane-modified phthalonitrile resin monomer is reduced to -12 to -35.6° C. due to the advantages of the polymer matrix of the phthalonitrile resin and the phthalonitrile resin. The obtained liquid phthalonitrile resin monomer can be directly coated on the fiber cloth at room temperature without dissolving in an organic solvent to prepare a phthalonitrile resin-based composite material prepreg.
为实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme that the present invention takes is as follows:
一种硅氧烷改性邻苯二甲腈树脂基复合材料，所述复合材料包括树脂基体和纤维增强材料；所述树脂基体的制备原料包括含硅氧烷结构的液态邻苯二甲腈单体(未固化)，化学结构式为：A siloxane-modified phthalonitrile resin-based composite material, the composite material includes a resin matrix and a fiber reinforcement; the preparation raw material of the resin matrix includes liquid phthalonitrile monomers containing a siloxane structure body (uncured), the chemical structural formula is:
进一步地，所述纤维增强材料为碳纤维布、玄武岩纤维布、石英纤维布和玻璃纤维布。Further, the fiber reinforced material is carbon fiber cloth, basalt fiber cloth, quartz fiber cloth and glass fiber cloth.
进一步地，所述树脂基体为液态硅氧烷改性邻苯二甲腈树脂单体与固化剂的混合物；所述固化剂为4，4-二氨基二苯砜、1，4-双(4-氨基苯氧基)苯、乙二胺和己二胺中的一种或几种。Further, the resin matrix is a mixture of a liquid siloxane modified phthalonitrile resin monomer and a curing agent; the curing agent is 4,4-diaminodiphenylsulfone, 1,4-bis(4 One or more of -aminophenoxy)benzene, ethylenediamine and hexamethylenediamine.
一种上述的硅氧烷改性邻苯二甲腈树脂基复合材料的制备方法，所述方法为：A kind of preparation method of above-mentioned siloxane modified phthalonitrile resin-based composite material, described method is:
步骤一：以液态硅氧烷改性邻苯二甲腈树脂单体与固化剂的混合物为预浸液，在室温下涂敷于纤维布表面，得到硅氧烷改性邻苯二甲腈树脂预浸布；Step 1: Use the mixture of liquid siloxane-modified phthalonitrile resin monomer and curing agent as a pre-preg liquid, and apply it on the surface of fiber cloth at room temperature to obtain siloxane-modified phthalonitrile resin prepreg;
步骤二：将多层预浸布进行叠层，得到硅氧烷改性邻苯二甲腈树脂预浸料；Step 2: Laminating multiple layers of prepregs to obtain siloxane-modified phthalonitrile resin prepregs;
步骤三：将预浸料进行热压和热固化成型处理，得到硅氧烷改性邻苯二甲腈树脂基复合材料。Step 3: subjecting the prepreg to hot pressing and thermosetting molding to obtain a siloxane-modified phthalonitrile resin-based composite material.
进一步地，步骤一中，所述液态硅氧烷改性邻苯二甲腈树脂单体与固化剂的质量比为100-150：1.5-10。Further, in step one, the mass ratio of the liquid siloxane-modified phthalonitrile resin monomer to the curing agent is 100-150:1.5-10.
进一步地，步骤一中，所述纤维布表面，预浸液的分散量为0.4-1.5g/cm3。Further, in step 1, the dispersion amount of the prepreg on the surface of the fiber cloth is 0.4-1.5 g/cm 3 .
进一步地，步骤二中，所述叠层的层叠数为5-15层。Further, in step 2, the number of stacked layers is 5-15 layers.
进一步地，步骤三中，所述热压成型包括：依次进行第一梯度热压成型、第二梯度热压成型和第三梯度热压成型；Further, in Step 3, the hot press forming includes: sequentially performing the first gradient hot press forming, the second gradient hot press forming and the third gradient hot press forming;
所述第一梯度热压成型为：在200～220℃条件下，依次进行保温3-5小时，升压至0.5-2MPa，保温保压0.5-2小时；The first gradient hot-press forming is: under the condition of 200-220°C, heat preservation for 3-5 hours in sequence, increase the pressure to 0.5-2MPa, and heat-preserve for 0.5-2 hours;
所述第二梯度热压成型为：在220-250℃条件下，升压至1.5-2MPa、保温1-2小时、升压至2-3MPa、保温2-4小时；The second gradient hot-press forming is: under the condition of 220-250°C, increase the pressure to 1.5-2MPa, keep the temperature for 1-2 hours, increase the pressure to 2-3MPa, and keep the temperature for 2-4 hours;
所述第三梯度热压成型为：升压至3-5MPa，并在3-5MPa压力下，依次进行在250-260℃下保压保温1-2小时、升温至260-280℃下保温3-5小时。The third gradient hot-press forming is: boosting the pressure to 3-5MPa, and under the pressure of 3-5MPa, successively carry out the pressure keeping at 250-260°C for 1-2 hours, and the temperature rising to 260-280°C for 3 -5 hours.
进一步地，步骤三中，所述热压成型的温度为200-280℃，压力为1.5-5MPa，时间为4-12h。Further, in step 3, the temperature of the hot press forming is 200-280° C., the pressure is 1.5-5 MPa, and the time is 4-12 hours.
本发明相对于现有技术的有益效果为：本发明使用硅氧烷改性邻苯二甲腈树脂与固化剂的混合液浸润纤维布表面，通过热压使纤维布成型，通过热固化的方式使浸渍于纤维布中的硅氧烷改性邻苯二甲腈树脂固化。本发明在200-280℃下进行硅氧烷改性邻苯二甲腈树脂与固化剂的固化。由于本发明方法不使用有机溶剂，避免了复合材料制备过程中有机溶剂对于施工人员的损伤以及对环境的污染；同时缩短了邻苯二甲腈树脂基纤维增强复合材料的制备流程，提高了复合材料的制备效率；此外还避免了复合材料由于制备过程中有机溶剂残留导致的孔隙率过高的问题，从而提高了复合材料的力学性能。该方法工艺简单，成本较低，适合工业化生产，该复合材料具有耐高温、强度高等优异的综合性能，可满足航空航天、船舶等领域的要求。Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention uses a mixture of siloxane-modified phthalonitrile resin and curing agent to infiltrate the surface of the fiber cloth, and forms the fiber cloth by hot pressing, and heat-cures The silicone-modified phthalonitrile resin impregnated in the fiber cloth is cured. In the invention, the curing of the siloxane-modified phthalonitrile resin and the curing agent is carried out at 200-280°C. Since the method of the present invention does not use organic solvents, the damage of organic solvents to construction personnel and the pollution to the environment during the preparation of composite materials are avoided; at the same time, the preparation process of phthalonitrile resin-based fiber-reinforced composite materials is shortened, and the composite material is improved. The preparation efficiency of the material; in addition, the problem of high porosity of the composite material due to the residual organic solvent in the preparation process is avoided, thereby improving the mechanical properties of the composite material. The method has simple process and low cost, and is suitable for industrial production. The composite material has excellent comprehensive properties such as high temperature resistance and high strength, and can meet the requirements of aerospace, shipbuilding and other fields.
具体实施方式Detailed ways
下面通过实施例对本发明的技术方案进行进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。The technical solution of the present invention will be further described below through the examples, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention within the scope of protection.
本发明复合材料以含硅氧烷结构的邻苯二甲腈化合物为树脂单体，基体树脂同时具有邻苯二甲腈结构和硅氧烷结构，因此兼具聚硅氧烷树脂与邻苯二甲腈树脂的优势，并且由于结构中硅氧烷结构的引入，使树脂基单体的玻璃化转变温度降低至-12～-35.6℃，可在常温下涂覆制备复合材料预浸料，同时无有机溶剂的使用，极大的缩短了邻苯二甲腈树脂基复合材料的制备工艺流程。此外，实施例结果表明，本发明所得邻苯二甲腈树脂基复合材料具有良好的力学性能，其在常温下弯曲强度为307MPa，层间剪切强度为25MPa；300℃下弯曲强度236MPa，层间剪切强度为13MPa，耐温性能好。The composite material of the present invention uses the phthalonitrile compound containing the siloxane structure as the resin monomer, and the matrix resin has the phthalonitrile structure and the siloxane structure at the same time, so it has both the polysiloxane resin and the phthalonitrile compound. The advantage of the nitrile resin, and due to the introduction of the siloxane structure in the structure, the glass transition temperature of the resin-based monomer is reduced to -12~-35.6°C, which can be coated at room temperature to prepare composite material prepregs, and at the same time The use of no organic solvent greatly shortens the preparation process of the phthalonitrile resin-based composite material. In addition, the results of the examples show that the phthalonitrile resin-based composite material obtained in the present invention has good mechanical properties, and its bending strength at room temperature is 307 MPa, and the interlaminar shear strength is 25 MPa; the bending strength at 300 ° C is 236 MPa, and the layer The inter-shear strength is 13MPa, and the temperature resistance is good.
实施例1：Example 1:
一种硅氧烷改性邻苯二甲腈树脂基复合材料，树脂基体的聚合单体为含硅氧烷结构的双邻苯二甲腈化合物(SiPN)，其结构式如下所示，增强材料为碳纤维布T300。A siloxane-modified phthalonitrile resin-based composite material, the polymerized monomer of the resin matrix is a diphthalonitrile compound (SiPN) containing a siloxane structure, its structural formula is as follows, and the reinforcing material is Carbon fiber cloth T300.
本实施例的硅氧烷改性邻苯二甲腈树脂基复合材料的制备方法包括以下步骤：将5wt％固化剂(1，4-双(4-氨基苯氧基)苯)与SiPN单体磁力搅拌混合均匀。将所得混合物涂覆于10块同样尺寸(5cm×5cm)的碳纤维布上，得到预浸料布。直接将预浸料布按同方向放入模具压实后放入平板硫化机，在无外压200℃下保温4h。调节硫化机加压至1MPa、升温至220℃持续保温1h；加压至2MPa、升温至250℃并持续保温1h后、加压至3MPa并保温3h；加压至5MPa后升温至260℃保温2h后，升温至280℃保温4h。取出模具自然冷却至室温后得到硅氧烷改性邻苯二甲腈树脂基复合材料板材(厚度为2.0±0.2mm)。The preparation method of the siloxane-modified phthalonitrile resin-based composite material of the present embodiment comprises the following steps: mixing 5wt% curing agent (1,4-bis(4-aminophenoxy)benzene) with SiPN monomer Mix evenly by magnetic stirring. The resulting mixture was coated on 10 carbon fiber cloths of the same size (5 cm×5 cm) to obtain a prepreg cloth. Put the prepreg cloth directly into the mold in the same direction for compaction, then put it into the flat vulcanizing machine, and keep it warm for 4 hours at 200°C without external pressure. Adjust the vulcanizer to pressurize to 1MPa, heat up to 220°C and keep warm for 1h; pressurize to 2MPa, heat up to 250°C and keep warm for 1h, pressurize to 3MPa and keep warm for 3h; pressurize to 5MPa, heat up to 260°C and keep warm for 2h Afterwards, the temperature was raised to 280° C. for 4 hours. After the mold was taken out and naturally cooled to room temperature, a siloxane-modified phthalonitrile resin-based composite sheet (thickness: 2.0±0.2 mm) was obtained.
实施例2：Example 2:
一种硅氧烷改性邻苯二甲腈树脂基复合材料，树脂基体的聚合单体为含硅氧烷结构的双邻苯二甲腈化合物(SiPN)，其结构式与实施例1相同，增强材料为碳玻璃纤维布T700。A siloxane-modified phthalonitrile resin-based composite material, the polymerized monomer of the resin matrix is a diphthalonitrile compound (SiPN) containing a siloxane structure, and its structural formula is the same as that of Example 1. The material is carbon glass fiber cloth T700.
本实施例的硅氧烷改性邻苯二甲腈树脂基复合材料的制备方法包括以下步骤：将5wt％固化剂(1，4-双(4-氨基苯氧基)苯)与SiPN单体磁力搅拌混合均匀。将所得混合物涂覆于10块同样尺寸(5cm×5cm)的玻璃纤维布上，得到预浸料布。将预浸料布按45°/0°/90°/-45°/-45°/90°/0°/45°的铺层方向放入模具压实后放入平板硫化机，在无外压200℃下保温5h。调节硫化机加压至1.5MPa、升温至220℃持续保温1h；加压至2MPa、升温至250℃并持续保温1h后、加压至2.5MPa并保温3h；加压至5MPa后升温至260℃保温1.5h后，升温至280℃保温5h。取出模具自然冷却至室温后得到硅氧烷改性邻苯二甲腈树脂基复合材料板材(厚度为2.0±0.2mm)。The preparation method of the siloxane-modified phthalonitrile resin-based composite material of the present embodiment comprises the following steps: mixing 5wt% curing agent (1,4-bis(4-aminophenoxy)benzene) with SiPN monomer Mix evenly by magnetic stirring. The resulting mixture was coated on 10 glass fiber cloths of the same size (5 cm x 5 cm) to obtain a prepreg cloth. Put the prepreg cloth into the mold according to the laying direction of 45°/0°/90°/-45°/-45°/90°/0°/45°, and then put it into the flat vulcanizing machine. Insulate at 200°C for 5 hours. Adjust the pressurization of the vulcanizer to 1.5MPa, heat up to 220°C and keep warm for 1h; pressurize to 2MPa, heat up to 250°C and keep warm for 1h, then pressurize to 2.5MPa and keep warm for 3h; pressurize to 5MPa and heat up to 260°C After 1.5 hours of heat preservation, the temperature was raised to 280°C for 5 hours of heat preservation. After the mold was taken out and naturally cooled to room temperature, a siloxane-modified phthalonitrile resin-based composite sheet (thickness: 2.0±0.2 mm) was obtained.
实施例3：Example 3:
一种硅氧烷改性邻苯二甲腈树脂基复合材料，树脂基体的聚合单体为含硅氧烷结构的双邻苯二甲腈化合物(SiPN)，其结构式与实施例1相同，增强材料为玻璃纤维布。A siloxane-modified phthalonitrile resin-based composite material, the polymerized monomer of the resin matrix is a diphthalonitrile compound (SiPN) containing a siloxane structure, and its structural formula is the same as that of Example 1. The material is glass fiber cloth.
本实施例的硅氧烷改性邻苯二甲腈树脂基复合材料的制备方法包括以下步骤：将5wt％固化剂(1，4-双(4-氨基苯氧基)苯)与SiPN单体磁力搅拌混合均匀。将所得混合物涂覆于10块同样尺寸(5cm×5cm)的玻璃纤维布上，得到预浸料布。直接将预浸料布按同方向放入模具压实后放入平板硫化机，在无外压200℃下保温4h。调节硫化机加压至1MPa、升温至220℃持续保温0.5h；加压至1.5MPa、升温至250℃并持续保温1h后、加压至3MPa并保温3h；加压至5MPa后升温至260℃保温1h后，升温至280℃保温5h。取出模具自然冷却至室温后得到硅氧烷改性邻苯二甲腈树脂基复合材料板材(厚度为2.0±0.2mm)。The preparation method of the siloxane-modified phthalonitrile resin-based composite material of the present embodiment comprises the following steps: mixing 5wt% curing agent (1,4-bis(4-aminophenoxy)benzene) with SiPN monomer Mix evenly by magnetic stirring. The resulting mixture was coated on 10 glass fiber cloths of the same size (5 cm x 5 cm) to obtain a prepreg cloth. Put the prepreg cloth directly into the mold in the same direction for compaction, then put it into the flat vulcanizing machine, and keep it warm for 4 hours at 200°C without external pressure. Adjust the vulcanizer to pressurize to 1MPa, heat up to 220°C and keep warm for 0.5h; pressurize to 1.5MPa, heat up to 250°C and keep warm for 1h, then pressurize to 3MPa and keep warm for 3h; pressurize to 5MPa and heat up to 260°C After 1 hour of heat preservation, the temperature was raised to 280° C. for 5 hours of heat preservation. After the mold was taken out and naturally cooled to room temperature, a siloxane-modified phthalonitrile resin-based composite sheet (thickness: 2.0±0.2 mm) was obtained.
实施例4：Example 4:
一种硅氧烷改性邻苯二甲腈树脂基复合材料，树脂基体的聚合单体为含硅氧烷结构的双邻苯二甲腈化合物(SiPN2)，其结构式如下所示，增强材料为碳纤维布T300。A siloxane-modified phthalonitrile resin-based composite material. The polymerized monomer of the resin matrix is a diphthalonitrile compound (SiPN2) containing a siloxane structure. Its structural formula is as follows, and the reinforcing material is Carbon fiber cloth T300.
本实施例的硅氧烷改性邻苯二甲腈树脂基复合材料的制备方法包括以下步骤：将5wt％固化剂(1，4-双(4-氨基苯氧基)苯)与SiPN2单体磁力搅拌混合均匀。将所得混合物涂覆于10块同样尺寸(5cm×5cm)的碳纤维布上，得到预浸料布。直接将预浸料布按同方向放入模具压实后放入平板硫化机，在无外压200℃下保温5h。调节硫化机加压至1.5MPa、升温至220℃持续保温1h；加压至2MPa、升温至250℃并持续保温1h后、加压至3MPa并保温3h；加压至5MPa后升温至260℃保温2h后，升温至280℃保温4h。取出模具自然冷却至室温后得到硅氧烷改性邻苯二甲腈树脂基复合材料板材(厚度为2.0±0.2mm)。The preparation method of the siloxane-modified phthalonitrile resin-based composite material of the present embodiment comprises the following steps: mix 5wt% curing agent (1,4-bis(4-aminophenoxy)benzene) with SiPN2 monomer Mix evenly by magnetic stirring. The resulting mixture was coated on 10 carbon fiber cloths of the same size (5 cm×5 cm) to obtain a prepreg cloth. Put the prepreg cloth directly into the mold in the same direction for compaction, then put it into the flat vulcanizing machine, and keep it warm for 5 hours at 200°C without external pressure. Adjust the vulcanizer to pressurize to 1.5MPa, heat up to 220°C and keep warm for 1h; pressurize to 2MPa, heat up to 250°C and keep warm for 1h, pressurize to 3MPa and keep warm for 3h; pressurize to 5MPa, heat up to 260°C and keep warm After 2h, the temperature was raised to 280°C for 4h. After the mold was taken out and naturally cooled to room temperature, a siloxane-modified phthalonitrile resin-based composite sheet (thickness: 2.0±0.2 mm) was obtained.
对实施例1-4所得硅氧烷改性邻苯二甲腈树脂基复合材料在室温、300℃下，采用万能试验机进行弯曲强度、层间剪切强度测试，所得结果列于表1中。The siloxane-modified phthalonitrile resin-based composite material obtained in Examples 1-4 was tested for flexural strength and interlaminar shear strength using a universal testing machine at room temperature and 300°C, and the results are listed in Table 1. .
表1实施例1-4所得硅氧烷改性邻苯二甲腈树脂基复合材料的力学性能The mechanical properties of the siloxane-modified phthalonitrile resin-based composite material obtained in table 1 embodiment 1-4
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化均应为等效的置换方式，都包含在本发明的保护范围内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, All simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.
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