Preparation of Polyurea Elastomer with Flame Retardant, Insulation and Thermal Conductivity Properties

By using 6,6-((sulfonylbis(4,1-phenylene)bis(azanediyl))bis(thiophen-2-ylm-ethylene))bis6H-di-benzo[c,e][1,2]oxaphosphinine 6-oxide(DOPO-N)as phosphorus-nitrogen flame retardant,the polyurea(PUA)with flame retardant properties(PUA/DOPO-N)was prepared.In addition,organically modified montmorillonite(OMMT)and magnesium hydroxide(MH)were used as co-effectors respectively,and the flame retardant PUA(PUA/DOPO-N/OMMT and PUA/DOPO-N/MH)were also prepared.Thermal properties,flame retardant properties,flame retardant mechanism and mechanical properties of PUA/DOPO-N,PUA/DOPO-N/OMMT and PUA/DOPO-N/MH were investigated by thermogravimetric(TG)analysis,limiting oxygen index(LOI),UL 94,cone calorimeter test,scanning electron microscopy(SEM),and tensile test.The results show that the LOI value of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are 27.1%,27.7%,and 28.3%,respectively,and UL 94 V-0 rating is attained.Compared with PUA,the peak heat release rate(pk-HRR),total heat release(THR)and average effective heat combustion(av-EHC)of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH decrease significantly.SEM results indicate that the residual chars of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are completer and more compact.The complex of DOPO-N/OMMT and DOPO-N/MH have synergistic flame retardancy.The mechanical properties of PUA can be improved by the addition of DOPO-N,DOPO-N/OMMT and DOPO-N/MH,respectively.The insulation performance test shows that the volume resistivity of PUA/20%DOPO-N is 6.25×10^(16)Ω.cm.Furthermore,by using modified boron nitride(MBN)as heat dissipating material,the complex of PUA/MBN was prepared,and the thermal conductivity of PUA/MBN was investigated.The thermal conductivity of PUA/8%MBN complex coating at room temperature is 0.166 W/(M·K),which is a 163%improvement over pure PUA.

Explosion resistance performance of reinforced concrete box girder coated with polyurea:Model test and numerical simulation

To study the anti-explosion protection effect of polyurea coating on reinforced concrete box girder,two segmental girder specimens were made at a scale of 1:3,numbered as G(without polyurea coating)and PCG(with polyurea coating).The failure characteristics and dynamic responses of the specimens were compared through conducting explosion tests.The reliability of the numerical simulation using LS-DYNA software was verified by the test results.The effects of different scaled distances,reinforcement ratios,concrete strengths,coating thicknesses and ranges of polyurea were studied.The results show that the polyurea coating can effectively enhance the anti-explosion performance of the girder.The top plate of middle chamber in specimen G forms an elliptical penetrating hole,while that in specimen PCG only shows a very slight local dent.The peak vertical displacement and residual displacement of PCG decrease by 74.8% and 73.7%,respectively,compared with those of specimen G.For the TNT explosion with small equivalent,the polyurea coating has a more significant protective effect on reducing the size of fracture.With the increase of TNT equivalent,the protective effect of polyurea on reducing girder displacement becomes more significant.The optimal reinforcement ratio,concrete strength,thickness and range of polyurea coating were also drawn.

Experimental investigation on weak shock wave mitigation characteristics of flexible polyurethane foam and polyurea

In recent years,explosion shock wave has been considered as a signature injury of the current military conflicts.Although strong shock wave is lethal to the human body,weak shock wave can cause many more lasting consequences.To investigate the protection ability and characteristics of flexible materials and structures under weak shock wave loading,the blast wave produced by TNT explosive is loaded on the polyurethane foam with the density of 200.0 kg/m3(F-200)and 400.0 kg/m3(F-400),polyurea with the density of 1100.0 kg/m^(3)(P-1100)and structures composed of the two materials,which are intended for individual protection.Experimental results indicate that the shock wave is attenuated to weak pressure disturbance after interacting with the flexible materials which are not damaged.The shock wave protective capability of single-layer materials is dependent on their thickness,density and microscopic characteristics.The overpressure,maximum pressure rise rate and impulse of transmitted wave decrease exponentially with increase in sample thickness.For the same thickness,F-400 provides better protective capability than F-200 while P-1100 shows the best protective capability among the three materials.In this study,as the materials are not destroyed,F-200 with a thickness more than10.0 mm,F-400 with a thickness more than 4.0 mm,and P-1100 with a thickness more than 1.0 mm can attenuate the overpressure amplitude more than 90.0%.Further,multi-layer flexible composites are designed.Different layer layouts of designed structures and layer thickness of the single-layer materials can affect the protective performance.Within the research range,the structure in which polyurea is placed on the impact side shows the optimal shock wave protective performance,and the thicknesses of polyurea and polyurethane foam are 1.0 mm and 4.0 mm respectively.The overpressure attenuation rate reached maximum value of 93.3%and impulse attenuation capacity of this structure are better than those of single-layer polyurea and polyurethane foam with higher areal density.

Preparation and Properties of Spray Polyurea Elastomer for Aquaculture Foam Floating Balls

[Objectives] This study was conducted to develop a polyurea elastomer which can be sprayed on the surface of expanded polystyrene (EPS) floating balls, so as to improve the surface strength and service life of the floating balls. [Methods] The effects of the types and amounts of isocyanate, chain extenders and polyether polyols on the gelation rate, adhesion and wear resistance of polyurea elastomer were investigated, and it was finally determined the preparation process of polyurea elastomer using liquid isophorone diisocyanate (IPDI) and amino-terminated polyether (D2000) as the main raw materials, dimethylthiotoluene diamine (E300) as the chain extender and silica as the wear resistance modifier through two-step solution polymerization of prepolymerization and chain extension. [Results] The physical properties and chemical resistance tests of spray polyurea elastomer showed that it had good physical properties and acid and alkali resistance, and could meet the requirements of spraying and protection of EPS floating ball surface in marine environment. [Conclusions] Polyurea elastomer coating can improve the aging resistance, wear resistance and acid and alkali resistance of EPS floating balls, and prevent them from being fragile and floating randomly to form marine floating garbage which results in "white pollution".

Analysis and design for the comprehensive ballistic and blast resistance of polyurea-coated steel plate

Fragments and blast waves generated by explosions pose a serious threat to protective structures.In this paper,the impact resistance of polyurea-coated steel plate under complex dynamic loading is analyzed and designed for improving comprehensive ballistic and blast resistance using the newly established computational evaluating model.Firstly,according to the thickness and placement effects of the coating on the impact resistance,the steel-core sandwich plates are designed,which are proved to own outstanding comprehensive ballistic and blast resistance.Besides,the distribution diagram of ballistic and blast resistance for different polyurea-coated steel plates is given to guide the design of protective structures applying in different explosion scenarios.Furthermore,the dynamic response of designed plates under two scenarios with combined fragments and blast loading is studied.The results show that the synergistic effect of the combined loading reduces both the ballistic and blast resistance of the polyurea-coated steel plate.Besides,the acting sequence of the fragments and blast affects the structural protective performance heavily.It is found that the first loading inducing structural large deformation or damage is dominant.When fragments impact first,the excellent unit-thickness ballistic performance of the structural front part is strongly needed for improving the comprehensive ballistic and blast resistance.

Experimental study of polyurea-coated fiber-reinforced cement boards under gas explosions

Five types of polyurea elastomers were synthesized by changing the isocyanate component and the mechanical properties of polyurea materials were measured. Fiber-reinforced cement boards(FRCB)strengthened by polyurea with different formulations were processed, and a series of experiments were carried out on the specimens with gas explosion devices. The results showed that the conventional mechanical properties of different types of polyureas had their own advantages. Based on the gas explosion overpressure criterion, the blast resistances of reinforced plates were quantitatively evaluated,and the best polyurea was selected to guide the formulation design. The three typical failure modes of polyurea-reinforced FRCBs were flexural, shear, and flexural-shear failure. Dynamic thermodynamics and shock wave spectral analysis revealed that the polyurea did not undergo a glass transition in the gas explosion tests but retained its elastic properties, allowing it to effectively wrap the fragments formed by the brittle substrates.

考虑多种作用效应的表面防渗聚脲涂层非线性分析及设计

聚脲与聚氨酯相比,具有绿色环保、耐久性好、力学性能优异、施工面适应性强等优势,聚脲基防渗层被广泛应用于水工结构中。鉴于防渗聚脲尚无成型的结构设计计算理论,惯常采用的经验性设计可能会导致不安全、不合理、不经济的设计结果,本研究通过探讨聚脲基表面防渗涂层非线性分析的关键理论,基于有限单元法建立了非线性数值模型。在涂层基面开裂、水压荷载作用、伸缩缝变形等不同受力工况下,通过对材料的受力变形行为、剥离行为、破坏模式等分析,总结了涂层受力变形规律,并基于分析结果,提出表面防渗聚脲设计流程。研究表明:对于水压作用下的涂层基面开裂工况,涂层最大应力随水压荷载、粘结强度增大而增大,随开裂宽度变化不显著,涂层剥离长度随粘结强度增大而减小,随开裂宽度增大而增大;对于伸缩缝变形工况,涂层剥离长度均随涂层厚度增大而增大,涂层剥离长度随伸缩缝变形量增大而增大,随粘结强度增大而减小,剥离长度随水压荷载变化趋势不显著;涂层最大应力随涂层厚度增大而减小,随粘结强度增大而增大,随水压荷载增大而逐渐增大。最终基于数值分析结果提出了考虑伸缩缝变形工况下的聚脲涂层结构设计方法,形成设计流程并计算机软件化。

改性埃洛石纳米管在聚脲基防火涂料中的应用研究

为了提高聚脲基防火涂料的防火性能,探究埃洛石纳米管对聚脲基涂料防火性能的影响,通过表面改性的方法,用甲基三甲氧基硅烷改性埃洛石纳米管,并将改性埃洛石纳米管引入到聚脲膨胀型防火涂料中,采用锥形量热仪、红外光谱分析仪、导热系数仪、场发射扫描电镜、透射扫描电镜、防火性能测试装置等对其进行表征分析。研究发现:添加质量分数为5%的改性埃洛石纳米管的涂料样品的热释放峰值为95.89 kW/m^(2),相较未添加的样品降低了38.48%;总的热释放量为7.20 MJ/m^(2),相较未添加的样品降低了76.50%;总的烟释放值为4.32 m^(2),相较未添加的样品降低了40.98%;常温下导热系数为0.067 W/(m·K),相较未添加的样品降低了17.30%;燃烧后样品残留物表面更加致密,强度更高,对烟热的释放有更好的抑制作用,表现出了优异的防火性能。实验结果表明,改性埃洛石纳米管在降低复合材料导热系数和基体树脂催化成炭方面起到了双重作用,对聚脲基防火涂料防火性能的提高起到了重要作用。

自润滑自修复双功能微胶囊的制备及工艺优化

采用原位聚合法制备了以聚脲甲醛(PUF)为壁材,亚麻油(LO)和1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)为芯材的双芯微胶囊,通过光学显微镜观察微胶囊的形成过程,研究了乳化剂种类、乳化剂含量、搅拌速度、芯壁比对微胶囊形貌和包覆率的影响,并确定了合成微胶囊的最佳工艺参数。结果表明:以聚乙烯醇为乳化剂,其用量为芯材含量的5%(质量分数),搅拌速度为600r/min,芯壁比为1∶1时制备的微胶囊外貌呈球型,表面无缺陷和孔洞,粒径分布均匀,平均粒径为20.29μm,壁厚为950nm且包覆率达到75.61%。

聚脲涂覆大型钢制储罐抗冲击性能数值仿真

为提高大型钢制储罐抗冲击性能,开展聚脲涂覆大型钢制储罐冲击响应的数值模拟和理论分析研究。基于前期工作已验证的数值模型,建立聚脲涂覆钢罐的有限元模型。数值模拟结果表明:将聚脲涂覆于罐体外表面能有效降低冲击载荷作用下局部塑性变形,在冲击体撞击角度为45°时能避免罐体穿孔破坏;聚脲涂层的主要防护机制为降速和垫层作用;提高喷聚脲涂厚度能增加罐体最大吸能值和面密度吸能值;当涂层厚度为15 mm时罐体不产生穿透破坏,满足英国储罐设计规范要求。根据罐体冲击响应特征和聚脲涂层作用机制,建立预测罐体断裂临界冲击速度的理论公式,能较精确预测涂覆罐的最大吸能值,可为聚脲涂覆钢制储罐抗冲击防护设计提供科学参考依据。

网格布-聚脲涂层耦合作用力学破坏机理研究

实际防渗工程中有时会将聚脲材料同网格布组合为复合防渗涂层,但其聚脲材料与网格布的耦合作用机理和破坏模式缺乏研究,而且该种复合涂层在实际应用中亦存在脱落、水解、耐久性差等问题。因此本文基于试验和数值分析,探讨网格布纤维同聚脲材料的耦合作用,考察网格布与聚脲涂层耦合作用的受力变形行为和破坏模式,分析不同纤维-基体材料组合形式下的变形性能和承载性能。研究结果表明:纤维断裂导致聚脲材料出现瞬间应力突变,纤维断裂面及应力突变引发的微裂纹导致整体截面拉断。聚脲材料强度较高,设置网格布后会导致涂层产生损伤缺陷,使得强度及伸长率大幅下降,伸长率降幅达到75%以上,因此网格布对聚脲材料性能起到负面效应。同样研究表明,聚氨酯材料强度相对较低,设置网格布后强度增幅约为14%,网格布对聚氨酯材料起到一定加强效果,但同样会导致伸长率大幅降低。由于网格布的伸长率及强度决定了复合涂层的伸长率及强度,因此在实际工程应用中,出现以下条件之一时不应在聚脲基体材料中设置网格布:(a)对止水防渗涂层伸长率要求高于网格布破坏伸长率;(b)基体材料强度大于网格布强度;(c)基体材料强度大于涂层-基面切向粘接强度。目前现有聚脲的相关标准及规范中的物理力学性能均未使用网格布进行加强,且科学定义的聚脲的相应标准及规范中所提的材料指标也均符合本研究所建议的不应加网格布的相应条件,因此建议工程中使用的聚脲材料不应设置网格布。

爆炸荷载下聚脲涂覆含局部缺陷油气管道的失效判定研究

通过埋地静爆试验,对经聚脲弹性体材料加固的含局部缺陷埋地油气管道抗爆性能及损伤评价进行研究,同时结合所得试验数据进行数值模拟,建立了浅埋爆炸荷载下聚脲弹性体材料加固含局部缺陷埋地油气管道损伤失效评估准则。结果表明:在折合距离为0.23 m/kg 1/3试验条件的浅埋爆炸荷载作用下,含局部缺陷普通管道与含局部缺陷聚脲管道迎爆面均发生了明显凹陷变形,含缺陷聚脲管道凹陷变形量较前者降低28.87%,且管道迎爆面及端部连接处易于遭受损伤;含局部缺陷普通管道迎爆面超压高于含局部缺陷聚脲管道且变形响应时间早于后者,表明聚脲材料可以有效降低爆炸冲击波压力峰值和推迟爆炸冲击波的作用时间。在进行爆炸荷载作用下管道的损伤失效判定时引入衡量管道横截面变形的截面临界椭圆度指标,最终建立了基于管道截面临界椭圆度的聚脲涂覆含局部缺陷埋地油气管道的超压-冲量损伤准则及判定公式。

聚脲润滑脂稠化剂对球轴承疲劳寿命的影响

采用光干涉法、动态击穿电压测试对3种聚脲润滑脂样品润滑膜厚进行了表征,同时测试了3种样品的轴承疲劳寿命和温升特性,对比研究了聚脲润滑脂稠化剂对润滑状态的影响,结果表明:聚脲润滑脂稠化剂在摩擦副表面吸附形成垫层,阻碍了润滑脂乏油润滑引起的润滑膜厚持续减小;聚脲润滑脂稠化剂的类型、含量对表面起源型剥落的轴承疲劳寿命有显著影响,合理的稠化剂配方可显著延长轴承疲劳寿命,这可能与聚脲润滑脂稠化剂的回流特性相关。

接触爆炸下聚脲涂层增强钢板的抗爆性能

为满足装甲车等武器装备在接触爆炸下的防护需求,通过实验与数值模拟开展单层钢板及迎/背爆面聚脲增强钢板接触爆炸下的抗爆性能研究,分析不同面密度、不同聚脲涂覆位置下钢板的破坏模式及防护机理,探究在一定面密度下钢板-聚脲厚度比对复合结构抗爆性能的影响。研究结果表明:背爆面涂覆等厚度聚脲能够有效减小钢板背面穿孔及拉伸破坏,降低结构残余位移,迎爆面涂覆等厚度聚脲能够显著增强结构抗爆能力,使接触爆炸下的钢板损伤大大降低;相同面密度下,聚脲吸能性能与聚脲厚度正相关,但是聚脲过厚会导致复合结构变形加大,稳定性降低;综合考虑聚脲增强钢板结构的破坏变形、速度衰减以及能量吸收情况,在研究范围内,钢板迎爆面涂覆厚度比为1∶0.78的聚脲层具有最佳的抗爆性能。

喷涂聚脲弹性体及复合结构抗爆抗冲击性能研究进展

防护结构的抗爆抗冲击性能是生命安全的重要保障,材料和结构是提高防护性能的2种主要途径。喷涂聚脲弹性体凭借良好的力学性能和耗能特性被广泛运用于抗爆抗冲击防护领域。从喷涂聚脲弹性体的抗冲击性能出发,介绍了不同试验方法下喷涂聚脲弹性体优异的爆炸冲击防护性能,分析喷涂聚脲弹性体在不同应变率和环境下良好的适应性,发现涂层厚度和涂层构造会对材料抗冲击性能产生影响;从材料微观层面以及阻抗失配的角度综述了喷涂聚脲弹性体的抗冲击机理,最后阐述了抗冲击复合结构的耗能机理以及优化方法,指出了喷涂聚脲弹性体以及复合结构尚存在的部分问题以及发展方向。

异氰酸酯硬段对聚脲弹性体性能的影响

异氰酸酯的分子结构对聚脲弹性体的理化性能影响巨大,为探究异氰酸酯分子结构的变化对聚脲弹性体自修复效率和力学强度的影响规律,选择了4种不同分子结构的异氰酸酯:异佛尔酮二异氰酸酯(IPDI)、4,4′-二异氰酸酯二环己基甲烷(HMDI)、4,4′-二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI),通过和聚醚胺反应得到了具有不同硬段结构的弹性体:SPU-IP、SPU-HM、SPU-M和SPU-H。通过红外光谱(FTIR)、X射线衍射(XRD)、动态热机械分析(DMA)和黏度等测试研究了异氰酸酯的分子结构对聚脲弹性体性能的影响机理。结果表明,具有刚性芳香和结晶硬片段的SPU-M和SPU-H,具有紧密的硬段结构域,材料力学强度更高,SPU-IP中不对称的脂环结构提供了足够的链迁移率,材料自修复性能更好。而SPU-M和SPU-IP自修复效率相当,由于SPU-M中苯环位阻较大,导致氢键化羰基大多以无序形式存在,增强了材料的自修复效率。

阻燃剂对喷涂聚脲弹性体阻燃性能的影响

选用阻燃剂次磷酸铝(AHP)、石墨(EG)、含磷多元醇按不同用量添加到喷涂聚脲弹性体(PUA)中,采用喷涂制样的方式制备阻燃聚脲,并探究了阻燃剂的种类及用量对聚脲热稳定性能和阻燃性能的影响。结果发现:AHP和EG的引入均能提高PUA的初始热分解温度和成炭性,含磷多元醇的引入会降低初始分解温度,对成炭性影响不大;通过石墨与含磷多元醇质量比1∶1复配会降低热释放速率和总释热量,改善成炭性和抑烟效果,LOI值可提高至29.2%,可达到UL94 V-0等级,阻燃性能优异。

喷涂聚脲及其纤维复合材料的抗侵彻性及防护机理研究新进展

在侵彻体高速冲切行为下,头盔和防弹衣等防护装备产生变形甚至穿透现象,且过往防护装备以金属、陶瓷为主,虽防护效果表现良好,但对人员敏捷性影响较大,因此轻量化成为设计防护装备的重要指标。喷涂聚脲和高性能纤维所具有的轻质高强等特性,足以满足防护基材的要求,因此将喷涂聚脲及纤维作为基材制作防护装备潜力巨大。本文首先从喷涂聚脲微相分离的结构特点入手,讲述分子链上软硬段以及氢键化的存在对材料性能的影响,介绍了喷涂聚脲的动态响应情况,分析认为在宽应变率范围下喷涂聚脲仍能保持性能稳定性。通过弹道实验发现喷涂聚脲受到侵彻体的高速冲切时会从橡胶态转变为玻璃态,对弹道极限具有提升作用;纤维的加入可以优化防护装备的结构整体性,复合材料损伤面积的扩大证明能量耗散水平的提高。最后从软硬段重排结晶、氢键作用等方面归纳分析喷涂聚脲的抗侵彻机理,并指出喷涂聚脲与纤维形成复合材料的重难点和亟待解决的问题。

环保型仲胺扩链剂在双组分聚脲防水涂料中的应用

仲胺扩链剂是双组分聚脲防水涂料配方体系中的关键原材料,其分子结构中的位阻基团可有效降低反应活性、改善操作性,提高配方容忍度,同时改善材料性能。本文重点介绍了3类环保型液体仲胺扩链剂在双组分喷涂聚脲防水涂料(芳香族、脂肪族)、双组分涂刷聚脲防水涂料(天冬聚脲、新型、黏弹型)共5个不同配方体系中的应用。

环氧树脂-改性聚氨酯及聚脲复合涂层的制备及防护性能研究

为了解决传统防护涂层材料单一、防护性能难以兼顾,单组分多元醇制备聚氨酯分子结构存在缺陷、聚脲固化速率过快的问题,通过改变聚氨酯合成原料中PTMG2000和聚醚3050的混合比例来调控聚氨酯交联、微相分离程度以改进其性能,同时采用P1000与扩链剂MDBA来制备可手工涂覆的慢反应聚脲,将环氧树脂作为底漆、聚氨酯-聚脲作为面漆,制备了一种具有优良耐磨、防腐、抗冲击等防护性能的涂层。结果表明:当m(PTMG2000)∶m(聚醚3050)=1∶2时制备的聚氨酯与PU-3050相比,其拉伸强度为13.19 MPa,提高了85.25%,伸长率为289.14%,提高了140%,热分解50%的温度从392.45℃提高到400.28℃,水接触角从90.72°增大到98.29°,综合性能得到提升。复合涂层在15 d中性盐雾测试后涂层未起泡、锈蚀面积小,高于ISO 9227-2006标准要求;附着力为0级,高于ISO 2409-2007标准要求的3级;抗冲击强度为100 cm,高于GB/T 1732-2020标准指定的最高50 cm冲击强度;在3.5%NaCl溶液中腐蚀9 d后阻抗维持在4.245×10^(7)Ω·cm^(2),30 min磨损量为10.28 mg,防护性能优异。