1、Challenges for Silica Tread Processing 白炭黑轮胎加工所面临的挑战,Dr.Lothar Steger /范汝良 Rhein Chemie Rheinau GmbH 莱茵化学（青岛）有限公司, 01.04.2019 ,Steger - Silica Tread I, Folie: 2 ,Why silica compounds ? 为何要发展白炭黑胎面？,By applying silica instead of carbon black in tire tread compounds the following results can be achieve
2、d : 用白炭黑代替炭黑具有如下优越性能： much lower rolling resistance of the tire 轮胎滚动损失降低很多 much better ice and snow performance 抗冰滑和抗雪滑行能优越很多 much better wet skid behaviour 抗湿滑性能改善很多 at similar tread wear patterns 具有相近的耐磨性,ABS-brake works only with silica on the wet road, 01.04.2019 ,Steger - Silica Tread I, Folie:
3、 3 ,Benefits of Silica Technology vs. Carbon Black白炭黑技术优势与炭黑比较,炭黑,白炭黑,滚动阻力,胎面寿命,抗湿滑性,抗雪滑性, 01.04.2019 ,Steger - Silica Tread I, Folie: 4 ,Properties of Silica with respect to Carbon Black 白炭黑与炭黑的性能对比,抗湿滑,抗雪/冰滑,滚动阻力,耐磨性, 01.04.2019 ,Steger - Silica Tread I, Folie: 5 ,History of silica technology 白炭黑技
4、术发展简史,1974 Blue silica tire developped by Metzeler / Germany High loading of silica and BR, no S-SBR available, insufficient processing equipment and know how 1975 Metzler stopped production of blue tire 1980- several developments: silanes, rubbers, 1990 processing equipment and processing know how
5、1992 Patent on Green Tire of Michelin / France S-SBR, less silica and BR, improved processing equipment and procedures 2000 State of the art silica tire achieves up to 30 % improvement of physical properties but has remarkable processing deficiencies, 01.04.2019 ,Steger - Silica Tread I, Folie: 6 ,U
6、p to 35 % reduced rolling resistance with silicaUp to 5 % less fuel consumption per caror approx. 2 billion litres of fuel savings per year in Germany alone,Green Tire Concept: Economic Benefit 绿色轮胎的概念：获得经济效益,使用白炭黑可使滚动阻力最多可降低35%,每辆轿车的耗油量最多可节省5%,仅在德国，每年可以节省20亿升的燃料,Green Tire Target for Economic Benef
7、it绿色轮胎的目标是获得经济效益, 01.04.2019 ,Steger - Silica Tread I, Folie: 7 ,Disadvantages of current silica technology 目前白炭黑技术的缺陷,1. Difficult to mix highly loaded silica compounds高填充白炭黑胶料门尼粘度较高难于加工 2. Long mixing cycles increase mixing costs长时间返炼/混炼，增加混炼成本 3. Temperature peaks during mixing lead to scorch pro
8、blems; 混炼温度高，易导致焦烧; 4. Parts of silane are absorbed in porous silica getting inefficient; 多孔的白炭黑吸收部分硅烷偶联剂，导致效率降低; 5. Manufacturers need to buy more powerful equipment. i.e. intermeshing rotors.加工者必须购买功率更高的设备，如：互齿式转子 (GKE密炼机), 01.04.2019 ,Steger - Silica Tread I, Folie: 8 ,Challenges for Silica Tread
9、 Processing 白炭黑轮胎加工所面临的挑战,1. Good Dispersion of High Dosage Silica高填充白炭黑的良好分散 2. Activation and Silanization of Silica白炭黑的活化和硅烷化反应 3. Coupling Reaction between Diene Silica and Rubbers白炭黑与二烯烃橡胶之间的偶联反应 4. New Curing Systems 新型硫化体系 5. More Powerful Equipment. i.e. intermeshing rotors.功率更高的设备，如：互齿式转子 (
10、GKE密炼机), 01.04.2019 ,Steger - Silica Tread I, Folie: 9 ,OEM Products Development for Silica Tire 白炭黑轮胎所需的配套产品开发,用于白炭黑的高效分散剂提高白炭黑的分散性 Aktiplast GT Aktiplast ST Aflux GE1837 白炭黑的有效硅烷偶联体系提高白炭黑的硅烷化反应程度和提高白炭黑与二烯烃橡胶的偶联反应程度 Si-69/Si-75 Silane + SASD 适合于高用量白炭黑的新型硫化体系 二烷基二硫代磷酸锌,Processing Promoters for Tire
11、Compound Processing 用于轮胎胶料的加工助剂,Dr.Lothar Steger /范汝良 Rhein Chemie Rheinau GmbH 莱茵化学（青岛）有限公司, 01.04.2019 ,Steger - Silica Tread I, Folie: 11 ,Processing Promoters : Definition 加工助剂的定义,Processing Promoters are tailer made additives, which enable a homogeneous mixing and the subsequent processing of t
12、he rubber compound“ 加工助剂是一种量身定做的添加剂，它们可以实现均相混炼并改善后续加工行为。 Processing Promoters improve the extrusion, calandering and molding performance but do not negatively influence the vulcanization properties of the mixture.“ 它们可以改善挤出、压延和模压硫化性能并且不会对硫化胶性能带来负面影响。, 01.04.2019 ,Steger - Silica Tread I, Folie: 12 ,
13、Correlation 生产过程与实验设备的相关性 Production and Laboratory Equipment,高压毛细管流变仪,门尼粘度,挤出机,流变硫化仪,模压硫化,混炼,挤出,注压硫化,剪切速率,粘度, 01.04.2019 ,Steger - Silica Tread I, Folie: 13 ,Division of Processing Promoters according to Their Chemical Composition 根据化学组成对加工助剂的分类, 01.04.2019 ,Steger - Silica Tread I, Folie: 14 ,Divi
14、sion of Processing Promoters according to their effects in the tire compound根据对轮胎胶料的影响的分类, 01.04.2019 ,Steger - Silica Tread I, Folie: 15 ,Processing Promoters with Mastication Effect具有塑炼效果的加工助剂, 01.04.2019 ,Steger - Silica Tread I, Folie: 16 ,Mastication Effect 塑炼效果Mooney Viscosity ML1+4/100C,Fatty
15、 Acid Fe-hemi,None,None,Zn-soap saturated Fe-hemi,Zn-soap Unsaturated Fe-hemi,Alk.-Poly-sulfide Fatty-acids Fe-hemi,NR, Internal Mixer, 3, dumped at 140，天然橡胶在密炼机中密炼3分钟排胶温度140 ,Aktiplast 8,Aktiplast M,Aktiplast F,Aflux 61,ML1+4/100C,无塑解剂,脂肪酸与铁络合物,饱和锌皂与铁络合物,不饱和锌皂与铁络合物,烷基多硫化物、脂肪酸与铁络合物, 01.04.2019 ,Steg
16、er - Silica Tread I, Folie: 17 ,Mode of Action of Processing Promoters 加工助剂的作用原理,内润滑作用,溶解于橡胶中,外润滑作用,不溶解于橡胶中,分散,润滑, 01.04.2019 ,Steger - Silica Tread I, Folie: 18 ,Processing Promoter Effects as a function of their polymer solubility溶解度不同加工助剂作用效果不同, 01.04.2019 ,Steger - Silica Tread I, Folie: 19 ,Pro
17、cessing Promoter Lubricant Effects 加工助剂的润滑作用,p p,crit,Vg,Vg,wall,Mixture,wall,Vg,Filmslippage膜滑动,high processing prom.,Concentration加工助剂浓度高,wall,Mixture,Effects at critical shear stress,with,active processing promoters,Effects at critical shear stress,without,processing promoter,Wall-Slip Wall-Stick
18、,Film-Slippage,不含加工助剂时临界剪切应力影响,含加工助剂时临界剪切应力影响, 01.04.2019 ,Steger - Silica Tread I, Folie: 20 ,Change of polymer conformation with shear stress 随剪切橡胶聚集体结构的变化,polymer chain orientation at high shear stress 高剪切应力下的橡胶分子链取向,Capillary Wall毛细管壁, 01.04.2019 ,Steger - Silica Tread I, Folie: 21 ,Analytical d
19、etermination of surface concentration 表面浓度的检测分析,Surface analysis via FTIR-Spectroscopy:,Sample,Calibration of the EPDM-Zinc- Soap mixture :,Characteristical pattern of the zinc soap : 1532 1/cm,Processing Promoter, 01.04.2019 ,Steger - Silica Tread I, Folie: 22 ,Processing Promoters Lubricant Effect
20、 加工助剂的润滑效果,Processing Promoters perform a certain function determined by their solubility in the rubber. 加工助剂润滑效果取决于它们在橡胶中的溶解度 They reduce shear stress due to high surface concentrations at location of high shear gradient. They resolve in the mix after leaving the shear zone (die). 加工助剂降低剪切应力，这是因为在高
21、剪切区域其浓度很高 Each polymer or blend needs its unique processing promoter taking into accaount the processing technique. 任何橡胶或其共混物都有与其相适应的加工助剂 Processing Promoetrs increase quality and quantity of extrusion and injection molding significantly. 加工助剂有效增加挤出、注射产品的质量和产量, 01.04.2019 ,Steger - Silica Tread I, F
22、olie: 23 ,Processing Promoter for Silica Tread Compounds 用于白炭黑胎面胶的加工助剂,Aktiplast ST,Aktiplast GT,Aflux GE1837, 01.04.2019 ,Steger - Silica Tread I, Folie: 24 ,Tread: Aktiplast GT in Carbon Black / E-SBR 莱茵塑分GT用于E-SBR/炭黑胎面,SBR 1712 110 BR-Buna CB 10 20 N-220 80 Aromatic Oil 10 Aktiplast GT 3 Stearic
23、acid 1 6PPD 1 TMQ 1 Wax/Antilux 654 2 Zn0 3 Sulfur 2,2 TBBS/Vukacit NZ 0,9,Processing Promoter : Aktiplast GT (Zn-soap / mainly saturated) Control without Processing Promoter 100 Mixing (Mooney, HPCR) ML 1+4/100C 85HPCR 100C/11s-1 85 Extrusion (Torsiograph) Extrusion rate g/min 104 Extrusion volume
24、cm/min 117 Curing (Rheovulcameter) Injection volume mm3 160 Injection speed mm3/sec 115 Literature ITEC 1998 Akron/OH Rhein Chemie Technical Report 63, 01.04.2019 ,Steger - Silica Tread I, Folie: 25 ,Tread: Aktiplast ST in Silica / S-SBR 莱茵塑分ST用于S-SBR/白炭黑胎面,S-SBR-Buna VSL 1955-S25 96 Nd-BR-Buna CB 2
25、4 30 Silica-Ultrasil 7000 70 Carbon Black N-110 10 X-50 S (50% Si-69) 12,5 Aktiplast ST 5 ZnO 3 Stearic acid 1 Aromatic Oil 20 TMQ 1 6PPD 1,5 Antilux 654 1,5 CBS 1,5 DPG 2 Sulphur 1,5,Processing Promoter : Aktiplast ST (mixture of Zn-soap, fatty-ester, filler) Control without Processing Promoter 100
26、 Mixing (Mooney, HPCR) ML 1+4/100C 83 HPCR 100C/11s-1 85 Extrusion (Torsiograph) Extrusion rate g/min 116 Extrusion volume cm/min 117 Curing (Rheovulcameter) Injection volume mm3 200 Injection speed mm3/sec 155 Literature ITEC 1996 Akron/OH Rhein Chemie Technical Report 60, 01.04.2019 ,Steger - Sili
27、ca Tread I, Folie: 26 ,Influence of Aktiplast ST Flow properties莱茵塑分ST对流动性的影响,0,10,20,30,40,50,60,0 phr,1 phr,2 phr,3 phr,4 phr,5 phr,0,500,1.000,1.500,2.000,2.500,0 phr,1 phr,2 phr,3 phr,4 phr,5 phr,0,5.000,10.000,15.000,20.000,25.000,0 phr,1 phr,2 phr,3 phr,4 phr,5 phr,0,10,20,30,40,50,60,70,80,0
28、phr,1 phr,2 phr,3 phr,4 phr,5 phr,HKR (90C,11/s),Viscosity (Pas),ML1+4100,Rheovulc. volume, 01.04.2019 ,Steger - Silica Tread I, Folie: 27 ,Formulation GEL 30437配方试验, 01.04.2019 ,Steger - Silica Tread I, Folie: 28 ,GEL 30437 MDR 160C硫化仪特性, 01.04.2019 ,Steger - Silica Tread I, Folie: 29 ,Viscosity ;
29、Mooney-Scorch门尼焦烧, 01.04.2019 ,Steger - Silica Tread I, Folie: 30 ,Physicals物性, 01.04.2019 ,Steger - Silica Tread I, Folie: 31 ,RPA2000 GEL 30437 RPA2000研究Payne效应,Control,Aktiplast ST,Aktiplast GT,Aflux GE 1837,Aflux GE 1837 Anti-sticky effect, 01.04.2019 ,Steger - Silica Tread I, Folie: 32 ,Advanta
30、ges of Aflux GE 1837 in S-SBR/silica 白炭黑分散助剂Aflux GE 1837的优点,Reduced compound viscosities降低混炼胶粘度 Improved flow properties in extrusion 改善挤出流动性 Improved flow properties in molding 改善模压流动性 Anti-sticky effect 具有防粘效果 Improved filler dispersion.改善填料分散 Lower energy use in extrusion and calandering降低挤出压延能耗
31、,Optimized compound processing without negative effect on product performance,Reaction Mechanism for Silica/Silane Technology 白炭黑/硅烷技术的反应机理,Dr.Lothar Steger /范汝良 Rhein Chemie Rheinau GmbH 莱茵化学（青岛）有限公司, 01.04.2019 ,Steger - Silica Tread I, Folie: 34 ,6.1 What is Silane?硅烷偶联剂的概念, 01.04.2019 ,Steger -
32、Silica Tread I, Folie: 35 ,6.2 Silane/Silica Coupling Reaction Dependent on Temperature and Time,硅烷偶联剂/白炭黑偶联反应依赖于温度和时间,TESPT: Si-69, 01.04.2019 ,Steger - Silica Tread I, Folie: 36 ,6.3 Silanization Reaction Mechanism 硅烷化反应机理, 01.04.2019 ,Steger - Silica Tread I, Folie: 37 ,6.5 Silane/Silica Diene Ru
33、bber Matrix Reaction Caused by Temperature 155 ,硅烷偶联剂/白炭黑、橡胶相反应温度155, 01.04.2019 ,Steger - Silica Tread I, Folie: 38 ,6.6 Sulfidosilane Reaction in Vulcanization 硫化过程中的偶联机理,The silane can react in the Sulfur vulcanization, 01.04.2019 ,Steger - Silica Tread I, Folie: 39 ,6.7 Interpenetrating Network
34、Theory 形成的互穿网络结构, 01.04.2019 ,Steger - Silica Tread I, Folie: 40 ,6.8 SEM Photograph of Silica-filled Rubber 白炭黑填充二烯烃橡胶的扫描电镜照片,Without silane,With silane, 01.04.2019 ,Steger - Silica Tread I, Folie: 41 ,6.9 Considerations When Using Silica/Silane Technology白炭黑/硅烷技术应用原理,1. More mixing is needed in no
35、n-productive steps compared toall carbon black compounds需要更多的混炼段数 2. Temperature control is importantDont be too high or too low混炼温度既不能太高也不能太低 3. TESPT (Si-69) have a limit of 160 of processing Si-69混炼温度不得超过160 4. TESPD (Si-75) enable better processing quality and speedSi-75混炼温度不得超过170 Slightly more
36、 coverage for the same weight of silane Higher processing temperatures are possible, typically up to 170 , so silanization reaction reaches more completion sooner It is possible to improve mixing times by 25 to 50%, 01.04.2019 ,Steger - Silica Tread I, Folie: 42 ,Working Mechanism of New Silane 新型硅烷
37、的反应机理,Working Mechanism of New Silane 新型硅烷的反应机理, 01.04.2019 ,Steger - Silica Tread I, Folie: 43 ,3. Silane + SASD improve blend & filler dispersion双组分新型硅烷改善混炼和填料分散,Silane + SASD,rubber matrix dispersed rubber phase dispersed silica phase,No diffusion control of curing chemicals causes bad physical p
38、roperties 不分散的硫化体系中的化学品，引起物性较差,Diffusion control of SASD achieves good physicals. Solubility is key factor SASD 控制分散，获得较好物性，可溶性是关键因素, 01.04.2019 ,Steger - Silica Tread I, Folie: 44 ,Mooney viscosity 门尼粘度 Dynamics动态性能 G little amplitude小振幅弹性模量 G big amplitude 大振幅弹性模量 “Payne”-effect Payne 效应 Silica-di
39、spersion 白炭黑分散Silanisation grade high = Mooney and G low.硅烷化反应程度越高 = 门尼粘度和弹性模量越低,Test of silanisation grade 硅烷化反应程度的测定, 01.04.2019 ,Steger - Silica Tread I, Folie: 45 ,Description of the dispersion process during mixing 混炼期间的白炭黑分散 Description of the silanisation process 硅烷化反应过程 Establishment of any
40、interaction between dispersion and silanisation 白炭黑分散和硅烷化反应之间的相互作用 Determining the most important process parameters 测定最重要的加工参数,Mixing of silica compounds 白炭黑胶料的混炼, 01.04.2019 ,Steger - Silica Tread I, Folie: 46 ,degree of dispersion is achieved in an early mixing stage 在前段混炼中已经获得优良的分散度 degree of di
41、spersion determinates final degree of silanisation 分散度确定了最终的硅烷化反应程度 Longer mixing times yield higher degree of silanisation 较长的混炼时间可获得较高的硅烷化反应程度 Higher mixing temperatures yield higher degree of silanisation 较高的混炼温度可获得较高的硅烷化反应程度 However at T 150 scorch is visible 但是，温度高于150时容易焦烧 Silane just slightly acts as a dispergator 硅烷偶联剂起到轻微的分散作用,Mixing of silica compounds 白炭黑胶料的混炼,Dithiophosphates Applications in Silica Tire 二硫代磷酸盐应用于白炭黑轮胎,Dr.Lothar Steger /范汝良 Rhein Chemie Rheinau GmbH 莱茵化学（青岛）有限公司,
