CN104742312A - 异质材料复合体的制备方法及由该方法制得的复合体 - Google Patents
异质材料复合体的制备方法及由该方法制得的复合体 Download PDFInfo
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Abstract
一种异质材料复合体,包括基体,该基体上形成有一氧化物层,该异质材料复合体进一步包括依次形成于该氧化物层表面的纳米膜及塑料件,该塑料件与该基体通过该氧化层及该纳米膜相结合。本发明还提供多种金属与塑料的复合成型体的成型方法。
Description
技术领域
本发明涉及多种异质材料复合体的制备方法及由该方法制得的异质材料复合体。
背景技术
在实际应用中,常常需要将金属和塑料进行连接形成复合体。现有的金属和塑料连接方法之一是采用粘接剂进行粘合,但通过粘接剂粘合无法制得长期有效及高强结合力的金属和塑料复合体。
另一种连接方法是先通过阳极氧化的方法在铝或铝合金等金属的表面成若干孔,然后将铝或铝合金放入模具内,注射塑料与铝或铝合金结合为一体。但上该方法仅可由可被阳极氧化的金属与塑料结合。同时因强酸遗留在若干孔内,会导致金属和塑料复合体易生锈且结合力不稳定。
发明内容
有鉴于此,有必要提供多种异质材料复合体的制备方法及由该方法制得的复合体。
一种异质材料复合体,包括基体,该基体上形成有一氧化物层,该异质材料复合体进一步包括依次形成于该氧化物层表面的纳米膜及塑料件,该塑料件与该基体通过该氧化层及该纳米膜相结合。
一种异质材料复合体,包括基体,该异质材料复合体进一步包括依次形成于基体表面的油墨层、纳米膜及塑料件,该塑料件与该基体通过该油墨层及该纳米膜相结合。
一种异质材料复合体的制备方法,其包括如下步骤:
提供一基体,所述基体的表面形成有一氧化物层;
对所述表面形成有氧化物层的基体进行硅烷化处理从而于氧化物层的表面形成一纳米膜,所述纳米膜具有三维网状结构;
将所述经硅烷化处理后的基体嵌入到一成型模具中,于所述模具中注射熔融的塑料并冷却,塑料覆盖于纳米膜的表面填充于纳米膜的三维网状结构中从而与基体结合。
一种异质材料复合体的制备方法,其包括如下步骤:
提供一基体;
于所述基体表面涂覆一油墨层;
对所述表面形成有油墨层的基体进行硅烷化处理从而于油墨层的表面形成一纳米膜,所述纳米膜具有三维网状结构;
将所述经硅烷化处理后的基体嵌入到一成型模具中,于所述模具中注射熔融的塑料并冷却,塑料覆盖于纳米膜的表面填充于纳米膜的三维网状结构中从而与基体结合。
相较于现有技术,上述异质材料复合体的制作方法通过将表面形成有氧化物的基体浸渍于成膜液中从而于氧化物层的表面形成纳米膜,塑料件通过该纳米膜及氧化物层与该基体牢固结合。上述异质材料复合体的制作方法还可通过将表面形成有油墨层的基体浸渍于成膜液中从而于油墨层的表面形成纳米膜,塑料件通过该纳米膜及油墨层与该基体牢固结合。上述两种异质材料复合体的制作过程中不使用有毒性溶剂,不会对环境、人体造成危害。
附图说明
图1为本发明第一较佳实施例异质材料复合体的剖视图。
图2为本发明第二较佳实施例异质材料复合体的剖视图。
图3为图1所示异质材料复合体的纳米膜的原子力显微镜照片。
图4为图2所示异质材料复合体的纳米膜的原子力显微镜照片。
主要元件符号说明
异质材料复合体 | 100 |
基体 | 11 |
氧化物层 | 13 |
纳米膜 | 15 |
塑料件 | 17 |
异质材料复合体 | 200 |
基体 | 21 |
油墨层 | 23 |
纳米膜 | 25 |
塑料件 | 27 |
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
请参阅图1,本发明第一较佳实施例的异质材料复合体100包括基体11及依次形成于基体11表面的氧化物层13、纳米膜15及塑料件17。
所述基体11可为不锈钢、铝、铝合金、铁、铁合金、铜、铜合金、钛、钛合金、镁或镁合金。
所述氧化物层13可为所述基体11于自然状态下形成的氧化物层。所述基体11的材质为不锈钢、铝、铝合金、铁、铁合金、铜或铜合金时,该不锈钢、铝、铝合金、铁、铁合金、铜或铜合金表面的氧化物层13经过化学抛光处理后的厚度可为5~15微米。此时,该基体11表面的氧化物层13可为氧化铁、氧化铝或氧化铜等。
该氧化物层13的氧化物可用MeO来表示,其中Me表示金属。该氧化物层13表层的氧化物可发生水解反应生成氢氧化物(未图示),该氢氧化物可用MeOH来表示。
所述基体11的材质为钛、钛合金、镁或镁合金时,无需对该基体11进行化学抛光处理,该基体11的氧化物层13的厚度可为5~15微米。此时,该基体11表面的氧化物层13可为氧化钛或氧化镁。
所述纳米膜15具有三维网状结构(参阅图3),其厚度可为3~15nm。该纳米膜15可呈现无色透明外观。该纳米膜15为碱性有机硅烷水解后形成的羟基与氧化物层13的表层水解后形成的氢氧化物发生硅烷化反应及水解后的碱性有机硅烷上未与氧化物层13表层的氢氧化物发生反应的羟基之间发生缩聚反应的反应产物。
该碱性有机硅烷中含有Si元素与烷基,其可用以下分子式来表示:R'(CH2)nSi(OR)3,其中R'代表有机官能团,OR代表可水解的基团,n代表CH2基团的个数。该有机官能团可为甲基、乙基、丁基、戊基等。
该碱性有机硅烷水解后形成的羟基与氧化物层13水解后形成的氢氧化物发生硅烷化反应后生成有Si-O-Me基团,该Si-O-Me基团可将该纳米膜15与该基体11通过Si-O-Me基团牢固结合。该水解后的碱性有机硅烷上未与氧化物层13表层的氢氧化物发生反应的羟基之间发生缩聚反应,使得该纳米膜15形成具有Si-O-Si基团的三维网状结构。
所述塑料件17通过注塑成型形成于纳米膜15的表面并渗入该纳米膜15的三维网状结构中,使得基体11通过氧化物层13及纳米膜15与塑料件17结合。
所述塑料件17可为聚对苯二甲酸丁二醇酯(PBT)、聚苯硫醚(PPS)、聚酰胺(PA)、聚丙烯(PP)、聚碳酸酯(PC)、丙烯腈-苯乙烯-丁二烯共聚物(ABS)、热塑性聚氨酯弹性体(TPU)、聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸1,4-环己烷二甲醇酯(PCT)等。
请参阅图2,本发明第二较佳实施例的异质材料复合体200包括基体21及依次形成于基体21表面的油墨层23、纳米膜25及塑料件27。
所述基体21可为金属或非金属。所述基体21为金属时,该金属可为不锈钢、铝、铝合金、铁、铁合金、铜、铜合金、钛、钛合金、镁或镁合金等。所述基体21为非金属时,该非金属可为玻璃、陶瓷或塑料等。
所述油墨层23的材质可为环氧树脂、聚酰胺树脂或丙烯酸树脂。所述油墨层23的厚度可为15~25微米。
可以理解的,所述油墨层23中掺杂有少量天然树脂。
所述纳米膜25具有三维网状结构(参阅图4),其厚度为3~15nm。该纳米膜25可呈现无色透明外观。
该纳米膜25为碱性有机硅烷水解后形成的羟基之间发生缩聚反应的反应产物。
该碱性有机硅烷中含有Si元素与烷基,其可用以下分子式来表示:R'(CH2)nSi(OR)3,其中R'代表有机官能团,OR代表可水解的基团,n代表CH2基团的个数。该有机官能团可为甲基、乙基、丁基、戊基等。
该水解后的碱性有机硅烷上的羟基之间发生缩聚反应,使得该纳米膜15形成具有Si-O-Si基团的三维网状结构。该纳米膜中含有Si-O-Si基团与烷基。
由于该纳米膜25中的烷基与油墨层23中的烷基具有相同或相近的结构,该纳米膜25与该油墨层23可根据相似相溶原理而牢固的结合,使得该纳米膜25可通过该油墨层23与基体21连接。
所述塑料件27通过注塑成型形成于纳米膜25的表面并渗入该纳米膜25的三维网状结构中,使得基体21通过油墨层23及纳米膜25与塑料件27结合。
所述塑料件27可为聚对苯二甲酸丁二醇酯(PBT)、聚苯硫醚(PPS)、聚酰胺(PA)、聚丙烯(PP)、聚碳酸酯(PC)、丙烯腈-苯乙烯-丁二烯共聚物(ABS)、热塑性聚氨酯弹性体(TPU)、聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸1,4-环己烷二甲醇酯(PCT)等。
本发明第一较佳实施例的异质材料复合体100的制备方法主要包括如下步骤:
提供经成型的基体11。所述基体11的材质可为不锈钢、铝、铝合金、铁、铁合金、铜或铜合金。此时,该基体11表面的氧化物层13可为氧化铁、氧化铝、氧化铜等。
所述基体11的表面于自然状态下形成有一氧化物层13。
对基体11进行脱脂除油清洗。该脱脂除油清洗主要包括将所述基体11浸渍于温度为55~65℃的脱脂液中5~12分钟以除去氧化物层13表面的油脂等杂质。脱脂除油清洗后对所述基体11进行水洗。所述脱脂剂可为市面上出售的常用的脱脂剂。
对所述经脱脂除油清洗后的基体11的表面进行化学抛光处理以提高氧化物层13的表面平整度。该经脱脂除油清洗后的氧化物层13的厚度可为5~15微米。
所述化学抛光处理可为:将基体11浸渍于一温度为90~100℃的化学抛光液中5~12秒。所述化学抛光液包括体积浓度为280~300g/L的硫酸与体积浓度为1150~1450g/L的磷酸。
可以理解的,当基体11为钛、钛合金、镁或镁合金时,该基体11表面的氧化物层13可为氧化钛或氧化镁。此时,无需对该基体11进行化学抛光处理,对基体11进行脱脂清洗后即可对该基体11进行硅烷化处理。该基体11表面的氧化物层13的厚度可为5~15微米。
对所述经化学抛光处理后的基体11的表面进行硅烷化处理从而于氧化物层13的表面形成纳米膜15。该纳米膜15具有三维网状结构,其厚度可为3~15nm。
所述硅烷化处理包括以下步骤:
将碱性有机硅烷加入水中制得一成膜液。该碱性有机硅烷与水的质量比可为1~3:30~100。该成膜液的pH可为8~9。该成膜液的保存期限为30~50天。该碱性有机硅烷中含有Si元素与烷基,其可用以下分子式来表示:R'(CH2)nSi(OR)3,其中R'代表有机官能团,OR代表可水解的基团,n代表CH2基团的个数。该有机官能团可为甲基、乙基、丁基、戊基等。
将基体11于室温下浸渍于该成膜液中5~10分钟,从而在基体11的氧化物层13的表面生成纳米膜15。所述室温的温度可为20~43℃。所述浸渍过程中,碱性有机硅烷会发生水解反应而带有羟基,其中,该碱性有机硅烷发生水解反应的反应方程式可为:
R'(CH2)nSi(OR)3 + 3H2O → R'(CH2)n-Si(OH)3+3ROH
氧化物层13表层的氧化物亦会发生水解反应形成氢氧化物使得基体11的表面带有羟基(该氧化物可用MeO来表示,氢氧化物可用MeOH来表示,其中Me表示金属),氧化物层13表层的氧化物发生水解反应的反应方程式可为:
MeO+ H2O → 2MeOH
氧化物层13表层的氢氧化物与水解后的碱性有机硅烷发生硅烷化反应从而形成Si-O-Me共价键,该Si-O-Me基团可将该纳米膜15与该基体11通过Si-O-Me基团牢固结合。该硅烷化反应的反应方程式可为:
水解后的碱性有机硅烷上未与氧化物层13表层的氢氧化物发生反应的羟基之间会发生缩聚反应从而形成具有Si-O-Si基团的三维网状结构的纳米膜15。该缩聚反应的反应方程式可为:
采用一原子力显微镜(未图示)对该基体11表面的纳米膜15进行观察,该原子力显微镜的测试结果显示该纳米膜15具有三维网状结构(参图3)。
将所述表面形成有纳米膜15的基体11嵌入到一成型模具(未图示)中,调节模温为40~150℃,射出温度为200~320℃,射出压力为1300~1700bar,射速为85~105mm/s。于所述成型模具中注射熔融的塑料,并于1350~1450bar的压力下保压1~2秒。塑料覆盖于纳米膜15的表面并渗透入该纳米膜15的三维网状结构中。该塑料冷却5~10秒后,该塑料件17与该基体11结合于一体,即获得该异质材料复合体100。
所述塑料件17可为聚对苯二甲酸丁二醇酯(PBT)、聚苯硫醚(PPS)、聚酰胺(PA)、聚丙烯(PP)、聚碳酸酯(PC)、丙烯腈-苯乙烯-丁二烯共聚物(ABS)、热塑性聚氨酯弹性体(TPU)、聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸1,4-环己烷二甲醇酯(PCT)等。
可以理解的,可根据实际生产的需要来调节塑料件17的厚度。
本发明第二较佳实施例的异质材料复合体200的制备方法主要包括如下步骤:
提供一基体21。所述基体21的材质可为金属或非金属。所述基体21为金属时,该金属可为不锈钢、铝、铝合金、铁、铁合金、铜、铜合金、钛、钛合金、镁或镁合金等。所述基体21为非金属时,该非金属可为玻璃、陶瓷或塑料等。
对该基体21进行除油清洗,以除去该基体21表面的油脂、灰尘等杂质。该除油清洗中用到的清洗剂可为市面上常见的弱碱性除油清洗剂。
于基体21表面涂覆一油墨层23。所述油墨层23的厚度可为15~25微米。
所述油墨层23的材质可为环氧树脂、聚酰胺树脂或丙烯酸树脂。
对所述表面形成有油墨层23的基体21进行硅烷化处理从而于油墨层23的表面形成一纳米膜25。该纳米膜25具有三维网状结构,其厚度为3~15nm。
所述硅烷化处理包括以下步骤:
将碱性有机硅烷加入水中制得一成膜液。该碱性有机硅烷与水的质量比可为1~3:30~100。该成膜液的pH可为8~9。该成膜液的保存期限为30~50天。加入至水中的碱性有机硅烷的部分基团会发生水解从而溶解于水中。该碱性有机硅烷中含有Si元素与烷基,其可用以下分子式来表示:R'(CH2)nSi(OR)3,其中R'代表有机官能团,OR代表可水解的基团,n代表CH2基团的个数。该有机官能团可为甲基、乙基、丁基、戊基等。
所述碱性有机硅烷中含有Si元素与烷基。该烷基可为甲基、乙基、丁基、戊基等。
将基体21于室温下浸渍于该成膜液中5~10分钟,从而在基体21的油墨层23的表面生成纳米膜25。所述室温的温度可为20~43℃。所述浸渍过程中,碱性有机硅烷会发生水解反应而带有羟基,其中,该碱性有机硅烷发生水解反应的反应方程式可为:
R'(CH2)nSi(OR)3 + 3H2O → R'(CH2)n-Si(OH)3+3ROH
该碱性有机硅烷水解后形成的羟基之间会发生缩聚反应形成具有Si-O-Si基团的纳米膜25,该纳米膜25具有三维网状结构。该纳米膜25中含有Si-O-Si基团与烷基。该缩聚反应的反应方程式可为:
由于该纳米膜25中的烷基与油墨层23中的烷基具有相同或相近的结构,该纳米膜25与该油墨层23可根据相似相溶原理而牢固的结合,使得该纳米膜25可通过该油墨层23与基体21连接。
采用一原子力显微镜(未图示)对该基体21表面的纳米膜25进行观察,该原子力显微镜的测试结果显示该纳米膜25具有三维网状结构(参图4)。
将所述表面形成有纳米膜25的基体21嵌入到一成型模具(未图示)中,调节模温为140~145℃,射出温度为250~275℃,射出压力为1300~1700bar,射速为85~105mm/s。于所述成型模具中注射熔融的塑料,并于1350~1450bar的压力下保压1~2秒。塑料覆盖于纳米膜25的表面并渗透入该纳米膜25的三维网状结构中。该塑料冷却5~10秒后,该塑料件27与该基体21结合于一体,即获得该异质材料复合体200。
所述塑料件27可为聚对苯二甲酸丁二醇酯(PBT)、聚苯硫醚(PPS)、聚酰胺(PA)、聚丙烯(PP)、聚碳酸酯(PC)、丙烯腈-苯乙烯-丁二烯共聚物(ABS)、热塑性聚氨酯弹性体(TPU)、聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸1,4-环己烷二甲醇酯(PCT)等。
可以理解的,可根据实际生产的需要来调节塑料件27的厚度。
对经上述方法制得的异质材料复合体100、200进行了抗拉强度及剪切强度测试。测试结果表明,该复合体100的抗拉强度可达3~8MPa,剪切强度可达21.5~24.6MPa。且对经上述测试后的复合体在进行冷热冲击试验(48小时,~40~85℃,4小时/cycle,12cycles)后发现,该复合体100、200的抗拉强度及剪切强度均无明显减小。
Claims (14)
1.一种异质材料复合体,包括基体,该基体上形成有一氧化物层,其特征在于:该异质材料复合体进一步包括依次形成于该氧化物层表面的纳米膜及塑料件,该塑料件与该基体通过该氧化层及该纳米膜相结合。
2.如权利要求1所述的异质材料复合体,其特征在于:该纳米膜为碱性有机硅烷水解后形成的羟基与氧化物层的表层水解后形成的氢氧化物发生硅烷化反应及水解后的碱性有机硅烷上未与氧化物层表层的氢氧化物发生反应的羟基之间发生缩聚反应的反应产物。
3.如权利要求1所述的异质材料复合体,其特征在于:所述纳米膜具有三维网状结构,其厚度为3~15nm,所述塑料件与该纳米膜结合并渗入所述网状结构中。
4.如权利要求1所述的异质材料复合体,其特征在于:所述基体为不锈钢、铝、铝合金、铁、铁合金、铜或铜合金时,该基体表面的氧化物层经过化学抛光处理后的厚度为5~15微米。
5.如权利要求1所述的异质材料复合体,其特征在于:所述基体为钛、钛合金、镁或镁合金时,该基体表面的氧化物层的厚度为5~15微米。
6.一种异质材料复合体,包括基体,其特征在于:该异质材料复合体进一步包括依次形成于基体表面的油墨层、纳米膜及塑料件,该塑料件与该基体通过该油墨层及该纳米膜相结合。
7.如权利要求6所述的异质材料复合体,其特征在于:所述纳米膜为碱性有机硅烷水解后形成的羟基之间发生缩聚反应的反应产物,该纳米膜中含有Si-O-Si基团与烷基。
8.如权利要求7所述的异质材料复合体,其特征在于:该油墨层中含有烷基,该油墨层中的烷基与该纳米膜中的烷基具有相同或相近的结构,使得该纳米膜与该油墨层牢固的结合。
9.如权利要求6所述的异质材料复合体,其特征在于:所述纳米膜具有三维网状结构,其厚度为3~15nm,所述塑料件与该纳米膜结合并渗入所述网状结构中。
10.如权利要求6所述的异质材料复合体,其特征在于:所述油墨层的材质为环氧树脂、聚酰胺树脂或丙烯酸树脂,其厚度为15~25微米。
11.一种异质材料复合体的制备方法,其包括如下步骤:
提供一基体,所述基体的表面形成有一氧化物层;
对所述表面形成有氧化物层的基体进行硅烷化处理从而于氧化物层的表面形成一纳米膜,所述纳米膜具有三维网状结构;
将所述经硅烷化处理后的基体嵌入到一成型模具中,于所述模具中注射熔融的塑料并冷却,塑料覆盖于纳米膜的表面填充于纳米膜的三维网状结构中从而与基体结合。
12.如权利要求11所述的异质材料复合体的制备方法,其特征在于:所述硅烷化处理包括以下步骤:将碱性有机硅烷加入水中制得一成膜液,该碱性有机硅烷与水的质量比为1~3:30~100,将基体于室温下浸渍于该成膜液中5~10分钟。
13.一种异质材料复合体的制备方法,其包括如下步骤:
提供一基体;
于所述基体表面涂覆一油墨层;
对所述表面形成有油墨层的基体进行硅烷化处理从而于油墨层的表面形成一纳米膜,所述纳米膜具有三维网状结构;
将所述经硅烷化处理后的基体嵌入到一成型模具中,于所述模具中注射熔融的塑料并冷却,塑料覆盖于纳米膜的表面填充于纳米膜的三维网状结构中从而与基体结合。
14.如权利要求13所述的异质材料复合体的制备方法,其特征在于:所述硅烷化处理包括以下步骤:将碱性有机硅烷加入水中制得一成膜液,该碱性有机硅烷与水的质量比可为1~3:30~100,将基体于室温下浸渍于该成膜液中5~10分钟。
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