CN113354919A - 一种软金属友好型树脂基摩擦材料及制备方法 - Google Patents
一种软金属友好型树脂基摩擦材料及制备方法 Download PDFInfo
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Abstract
本发明涉及一种软金属友好型树脂基摩擦材料及制备方法，以Ph为8.5的缓冲液，加入盐酸多巴胺和六方氮化硼混合，得到表面均匀包覆聚多巴胺纳米薄膜的改性氮化硼。然后将改性氮化硼作为填料同纤维、树脂粘结剂均匀混合，热压固化得到一种软金属友好型树脂基摩擦材料。有益效果为：提升了树脂基摩擦材料的减磨润滑性能、导热性能及抗剪切性能。树脂基摩擦材料的磨损率降低76％，软金属对偶盘的磨损率降低55.6％，摩擦过程中对偶盘表面温度明显下降。
Description
技术领域
本发明属于干式树脂基摩擦材料及制备方法，涉及一种软金属友好型树脂基摩擦材料及制备方法。
背景技术
在一些特定工程环境中，由于经济性需要或对材料导热、耐腐蚀等性能的高要求，常常应用到低硬度金属作为对偶盘，常见的如摩托车离合器中的铝对偶，以及海上挖泥船、深海钻机平台等大功率集热式摩擦装置中的铜对偶。但这些金属本身质软，易在摩擦过程中发生粘附和磨粒磨损。在持续制动过程中，低硬度对偶盘受到摩擦材料表面的微凸体及磨屑作用，更易产生划痕。此外，软金属还存在耐热性差、高温易氧化等缺陷，持续的摩擦热会使其强度进一步降低，耐磨性较差。为了减少对偶盘的受损，需要对摩擦材料进行优化设计。
树脂基摩擦材料具有性能可调、工艺流程简单、成本低、耐磨性好、使用寿命长等优点，广泛应用于工程机械、石油钻井和大型船舶等高速重载领域。但其与软金属对磨中，摩擦稳定性、磨损率以及对偶盘损伤程度等仍需进一步改善。
文献1“专利公开号CN 107353638 B的中国专利”公开了一种造粒氧化锆填充的树脂基摩擦材料的制备方法。该方法通过造粒工艺，得到一种具有纳米结构的氧化锆颗粒。按照重量百分比称取芳纶浆粕、造粒氧化锆、酚醛树脂等组分原料。将原料按照一定顺序投入到混料机中搅拌均匀得到混合料，将混合料放入钢模具中进行硫化处理即可得到造粒氧化锆填充的树脂基摩擦材料。该方法制备的树脂基摩擦材料制备工艺简单，具有摩擦系数高且稳定，抗热衰退性能优异的特点，但由于引入了硬质氧化锆颗粒，更容易对对偶材料，特别是软金属对偶造成损伤。
文献2“专利公开号CN 110540662 A的中国专利”公开了一种聚多巴胺改性碳纤维/莫来石晶须增强树脂基摩擦材料的制备方法。该方法通过多巴胺的自氧化聚合反应在莫来石晶须表面沉积纳米级聚多巴胺颗粒，将改性后的莫来石晶须和碳纤维与酚醛树脂混料后热压制备出树脂基摩擦材料。该树脂基制备的摩擦材料摩擦系数高、磨损量低、噪音低且耐热性优异，但是尚未涉及与铜铝等软金属摩擦制动产生的性能影响。
文献3“专利公开号CN 110102754 B的中国专利”公开了一种重载车辆干式离合器用铜基粉末冶金摩擦材料的制备方法。该方法优化了多种碳材料(石墨颗粒、石油焦炭和鳞片石墨)的成分和粒度，辅以合适配比的金属和陶瓷摩擦组元(铬铁粉、氧化锆粉、二氧化硅粉)通过粉末冶金方法制得铜基摩擦材料。该方法获得的摩擦材料尺寸稳定，具有良好的耐磨性、摩擦稳定性和不损伤对偶盘的优点。但粉末冶金方法耗能较大，没有树脂基摩擦材料环保节能。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种软金属友好型树脂基摩擦材料及制备方法，通过添加表面改性的六方氮化硼可提高树脂基摩擦材料的导热自润滑性能，有效降低了低硬度对偶材质(如铜、铝对偶)的磨损率，同时缓解了大功率持续制动条件下的摩擦生热的问题。
技术方案
一种软金属友好型树脂基摩擦材料，组份为增强纤维10-35％、填料20-35％、粘结剂20-40％、六方氮化硼1-5％；其特征在于：所述六方氮化硼采用改性六方氮化硼；以多巴胺吸附性使其在氮化硼表面发生自聚合反应得到改性六方氮化硼。
所述六方氮化硼的粒径为70-100nm，呈层片状结构，莫氏硬度为1-2。
一种制备所述软金属友好型树脂基摩擦材料的方法，其特征在于步骤如下：
步骤1、对六方氮化硼改性：将三羟甲基氨基甲烷与浓盐酸配制成pH为8.5的缓冲液，加入盐酸多巴胺和氮化硼室温搅拌，利用多巴胺吸附性使其在氮化硼表面发生自聚合反应得到改性后六方氮化硼；对改性六方氮化硼过滤洗涤，在60-80℃温度中真空干燥；
步骤2、按质量百分比称取原料：增强纤维10-35％、填料20-35％、粘结剂20-40％、改性六方氮化硼1-5％：
步骤3：将改性六方氮化硼与粘结剂进行球磨预混，再将预混物与增强纤维和填料放入高速混料机中均匀混合，得到絮状均匀混合原料；
步骤4：将混合原料填充至钢制模具中进行热压固化，在5-10MPa压力、160℃温度下热压600-800s，每50s放气一次，得到环状物质；
步骤5、进行热处理：热处理顺序依次为：100-120℃条件下保温60min，130℃-140℃条件下保温90min，145-165℃条件下保温120min，170-195℃条件下保温60min；获得软金属友好型树脂基摩擦材料。
所述步骤1中盐酸多巴胺的加入比例为2g/L，六方氮化硼的加入比例为10-20g/L。
所述步骤1中加入盐酸多巴胺和六方氮化硼室温搅拌24h。
所述步骤3中球磨预混3小时。
所述增强纤维是木纤维、玻璃纤维、碳纤维、芳纶纤维或矿物纤维的一种或任几种。
所述填料是矿粉、萤石粉、碳酸钙、硫酸钡、硅藻土、炭黑、黑胶粉的一种或几种。
所述粘结剂是改性酚醛树脂、聚酰亚胺树脂、环氧树脂、丁腈橡胶、硅橡胶的一种或几种。
有益效果
本发明提出的一种软金属友好型树脂基摩擦材料及制备方法，以Ph为8.5的缓冲液，加入盐酸多巴胺和六方氮化硼混合，得到表面均匀包覆聚多巴胺纳米薄膜的改性氮化硼。然后将改性氮化硼作为填料同纤维、树脂粘结剂均匀混合，热压固化得到一种软金属友好型树脂基摩擦材料。
由于六方氮化硼具有与石墨类似的层片状结构，硼原子和氮原子通过层内强共价键结合，层间则为较弱的范德华力，通过超声、溶剂处理可以逐层剥离得到单层氮化硼纳米片。其莫氏硬度仅为1-2，既具有常规陶瓷低密度、耐腐蚀和耐高温等共性，同时有高机械强度和化学稳定性，良好的润滑性能和导热性能。
在氮化硼表面包覆聚多巴胺纳米薄膜有利于其在基体中均匀分散，同时引入了多巴胺的氨基、羟基等多官能团，可以促进酚醛树脂的交联固化，提高机械强度，降低摩擦材料的磨损率。
有益效果为：提升了树脂基摩擦材料的减磨润滑性能、导热性能及抗剪切性能。树脂基摩擦材料的磨损率降低76％，软金属对偶盘的磨损率降低55.6％，摩擦过程中对偶盘表面温度明显下降。
所以本发明制备的树脂基摩擦材料抗剪切强度大幅提升，同时摩擦材料与对偶的磨损率均有显著降低，连续制动过程中的摩擦热可快速传导、扩散。
附图说明
图1为偏光显微镜下铜对偶盘磨损形貌
a为对比例，b为实例3
具体实施方式
现结合实施例、附图对本发明作进一步描述：
实施例1：
步骤一：量取500ml去离子水，使用三羟甲基氨基甲烷与浓盐酸调节溶液PH为8.5，先后加入1g盐酸多巴胺与10g六方氮化硼，室温搅拌24小时。之后对六方氮化硼进行过滤洗涤，60-80℃真空干燥箱中烘干，得到表面改性的氮化硼粉末。
步骤二：称取增强纤维24.00g，酚醛树脂12.00g，丁腈橡胶8.00g，填料与摩擦性能调节剂56.00g。其中，填料包含改性后氮化硼1.00g，碳酸钙7.00g。将上述原料进行高速混料，得到絮状混合物。
步骤三：称取絮状混合物15.47g，均匀填入钢制模具中，于压力5MPa、温度160℃下热压600s，得到厚度为3mm左右，密度为2g/cm3的环状预制体。
步骤四：将环状预制体放入鼓风干燥箱中进行热处理，热处理处理条件为120℃、60min-140℃、90min-160℃、120min-180℃、60min。热处理结束后，即获得改性后的树脂基摩擦材料。
实施例2：
步骤一：量取500ml去离子水，使用三羟甲基氨基甲烷与浓盐酸调节溶液PH为8.5，先后加入1g盐酸多巴胺与10g六方氮化硼，室温搅拌24小时。之后对六方氮化硼进行过滤洗涤，60-80℃真空干燥箱中烘干，得到表面改性的氮化硼粉末。
步骤二：称取增强纤维24.00g，酚醛树脂12.00g，丁腈橡胶8.00g，填料与摩擦性能调节剂56.00g。其中，填料包含改性后氮化硼3.00g，碳酸钙5.00g。将上述原料进行高速混料，得到絮状混合物。
步骤三：称取絮状混合物15.47g，将其均匀填入钢制模具中，将模具于压力5MPa、温度160℃下热压600s，得到厚度为3mm左右，密度为2g/cm3的环状预制体。
步骤四：将环状预制体放入鼓风干燥箱中进行热处理，热处理处理条件为120℃、60min-140℃、90min-160℃、120min-180℃、60min。热处理结束后，即获得改性后的树脂基摩擦材料。
实施例3：
步骤一：量取500ml去离子水，使用三羟甲基氨基甲烷与浓盐酸调节溶液PH为8.5，先后加入1g盐酸多巴胺与10g六方氮化硼，室温搅拌24小时。之后对六方氮化硼进行过滤洗涤，60-80℃真空干燥箱中烘干，得到表面改性的氮化硼粉末。
步骤二：称取增强纤维24.00g，酚醛树脂12.00g，丁腈橡胶8.00g，填料与摩擦性能调节剂56.00g。其中，填料包含改性后氮化硼5.00g，碳酸钙3.00g。将上述原料进行高速混料，得到絮状混合物。
步骤三：称取絮状混合物15.47g，将其均匀填入钢制模具中，将模具于压力5MPa、温度160℃下热压600s，得到厚度为3mm左右，密度为2g/cm3的环状预制体。
步骤四：将环状预制体放入鼓风干燥箱中进行热处理，热处理处理条件为120℃、60min-140℃、90min-160℃、120min-180℃、60min。热处理结束后，即获得改性后的树脂基摩擦材料。
步骤四：将环状预制体放入鼓风干燥箱中，进行梯度热处理，处理条件为120℃、60min-140℃、90min-160℃、120min-180℃、60min。热处理结束后，即获得改性后的树脂基摩擦材料。
对比例：传统方法制备的树脂基摩擦材料，即不含改性氮化硼。用碳酸钙代替以上加入的改性氮化硼。
将各实施例及对比例中所制得的试样进行性能检测，使用万能试验机测试其剪切强度，使用MM3000型摩擦磨损试验机测试其摩擦磨损性能。磨损率在室温风冷环境测量，0.5MPa压力、2000r/min转速下连续制动300次，制动间隔为15s。对偶盘表面温度在初始温度为室温时连续制动10次后测量，此处虽不等于摩擦界面的实际温度但代表了摩擦表面的温度变化趋势，进而反映摩擦材料的传热散热能力。检测结果如表1所示。
表1：不同实施例中树脂基摩擦片的性能检测结果
由表1的检测数据可知，添加表面聚多巴胺改性的氮化硼可以提升树脂基摩擦材料的抗剪切强度和促进摩擦热的传导、扩散；既降低树脂基摩擦材料的磨损率，又减少了对偶盘的损伤。该方法制得的树脂基摩擦材料性能优异，对低硬度金属有较好的保护作用，具备良好的应用前景。
Claims (9)
1.一种软金属友好型树脂基摩擦材料，组份为增强纤维10-35％、填料20-35％、粘结剂20-40％、六方氮化硼1-5％；其特征在于：所述六方氮化硼采用改性六方氮化硼；以多巴胺吸附性使其在氮化硼表面发生自聚合反应得到改性六方氮化硼。
2.根据权利要求1所述的软金属友好型树脂基摩擦材料，其特征在于：所述六方氮化硼的粒径为70-100nm，呈层片状结构，莫氏硬度为1-2。
3.一种制备权利要求1或2所述软金属友好型树脂基摩擦材料的方法，其特征在于步骤如下：
步骤1、对六方氮化硼改性：将三羟甲基氨基甲烷与浓盐酸配制成pH为8.5的缓冲液，加入盐酸多巴胺和氮化硼室温搅拌，利用多巴胺吸附性使其在氮化硼表面发生自聚合反应得到改性后六方氮化硼；对改性六方氮化硼过滤洗涤，在60-80℃温度中真空干燥；
步骤2、按质量百分比称取原料：增强纤维10-35％、填料20-35％、粘结剂20-40％、改性六方氮化硼1-5％：
步骤3：将改性六方氮化硼与粘结剂进行球磨预混，再将预混物与增强纤维和填料放入高速混料机中均匀混合，得到絮状均匀混合原料；
步骤4：将混合原料填充至钢制模具中进行热压固化，在5-10MPa压力、160℃温度下热压600-800s，每50s放气一次，得到环状物质；
步骤5、进行热处理：热处理顺序依次为：100-120℃条件下保温60min，130℃-140℃条件下保温90min，145-165℃条件下保温120min，170-195℃条件下保温60min；获得软金属友好型树脂基摩擦材料。
4.根据权利要求3所述的方法，其特征在于：所述步骤1中盐酸多巴胺的加入比例为2g/L，六方氮化硼的加入比例为10-20g/L。
5.根据权利要求3所述的方法，其特征在于：所述步骤1中加入盐酸多巴胺和六方氮化硼室温搅拌24h。
6.根据权利要求3所述的方法，其特征在于：所述步骤3中球磨预混3小时。
7.根据权利要求3所述的方法，其特征在于：所述增强纤维是木纤维、玻璃纤维、碳纤维、芳纶纤维或矿物纤维的一种或任几种。
8.根据权利要求3所述的方法，其特征在于：所述填料是矿粉、萤石粉、碳酸钙、硫酸钡、硅藻土、炭黑、黑胶粉的一种或几种。
9.根据权利要求3所述的方法，其特征在于：所述粘结剂是改性酚醛树脂、聚酰亚胺树脂、环氧树脂、丁腈橡胶、硅橡胶的一种或几种。
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