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First, the source and significance of the topic.
This topic mainly comes from the tutor's research topic.
With the development of modern science and technology, recombination has become an inevitable law of material development. In recent years, the research of nanocomposites has developed rapidly, and people have carried out a lot of experimental research work from the perspective of academic research and industrial production. The so-called nanocomposites were put forward by Roy et al in the early 1980s, which means that at least one dimension of the dispersed phase in the composites is less than 100nm. Nanoparticles have many special properties, such as small size effect, interface effect caused by large specific surface area, quantum effect and so on. Therefore, they can endow nanocomposites with many special properties and provide new opportunities for designing and preparing high-performance and multifunctional new materials. Nano-composite materials are known as "the most promising materials in 2 1 century" and have become one of the hot spots in materials science research.
Polymer/layered silicate (PLS) nanocomposites are one of the important research directions in the field of nanocomposites. PLS nanocomposites not only have the characteristics of light weight, corrosion resistance, good insulation and easy processing of polymer materials, but also have the advantages of high strength, high modulus and high heat resistance of inorganic materials, and have broad development prospects. PLS nanocomposites not only have the properties of ordinary nanocomposites, but also have obviously improved heat resistance, dimensional stability, gas barrier and flame retardancy due to its unique layered structure on the nanometer scale. The research and development of PLS nanocomposites has greatly improved the properties of traditional polymer materials and broadened the application scope of polymer materials.
According to the microstructure of composites, composites can be divided into four categories: composites filled with particles with poor compatibility; Ordinary particle filled composites: intercalated nanocomposites; Stripping the nanocomposite. Only the third and fourth kinds of composite materials have achieved nano-scale intercalation, and the fourth kind of composite materials, that is, exfoliated nanocomposites, have achieved remarkable nano-scale effect and higher interfacial bonding strength because of the sufficient and uniform dispersion of inorganic substances in the polymer matrix. This kind of composite material has excellent mechanical properties and heat resistance, and the barrier property of the material has been improved, which is the main research direction at present.
PLS nanocomposites have attracted more and more attention for their excellent properties. At present, PLS nanocomposites have developed from the basic research stage to the industrial production stage, and the commercial products of PLS nanocomposites have been developed by Toyota, Unitsika and Southernay in the United States.
In this paper, the layered silicate minerals (bentonite) and polymer raw materials in the province were used to modify the polymer raw materials, and the bentonite raw materials were further processed. The relationship between the composite mechanism, crystallization process, interface characteristics and structural properties of polymer and layered silicate, as well as the influence of processing and preparation technology on the properties of PLS nanocomposites and the determination of the best preparation process parameters were studied. Through reasonable processing technology, exfoliated nanocomposites with excellent properties were prepared. This is not only the characteristic and innovation of this subject, but also the research and development trend of nanocomposites.
Secondly, the research level and development trend in this field at home and abroad are briefly described.
Polymer/layered silicate nanocomposites are the most potential nanocomposites among many inorganic nano-particle modified composites, and they are also the most researched and most promising polymer nanocomposites for industrial production. Since 1987, the R&D Center of Toyota Company in Japan first reported the preparation of nylon 6/ clay nanocomposites by intercalation polymerization, polymer/clay nanocomposites have achieved nano-phase dispersion, strong interfacial interaction and self-assembly, and have incomparable advantages over traditional polymer/inorganic filler composites (such as excellent mechanical, thermal and gas barrier properties), so they have attracted much attention.
It is reported that the output value of PLS nanocomposites is expected to increase by about 100% every year in the future. By 2009, the output value will reach 65.438+0.5 billion euros/year, and the output will reach 500,000 tons/year. PLS nanocomposites will be widely used in all aspects of people's lives, and industries such as airplanes, automobiles, packaging, electronic appliances, building materials and furniture will benefit from this new material.
1, research status of PLS nanocomposites abroad
Since Okada et al reported PA6/ layered silicate nanocomposites in the late 1980s, great progress has been made in this field and it has become a new hotspot of polymer materials. So far, Toyota Research Center in Japan, Cornell University in the United States, University of Michigan and Institute of Chemistry of Chinese Academy of Sciences have conducted in-depth scientific research in this field.
1987, Fukushima and Inagaki of Toyota Center R&D Company carefully studied polymer/layered silicate composites, and replaced inorganic ions between clay layers with quaternary ammonium salt, which successfully improved the compatibility between clay and polymer matrix and developed PLS nylon 6/ silicate nanocomposites. The thermal deformation temperature of the material is much higher than that of pure nylon 6, and the mechanical properties and barrier properties are improved to varying degrees. Usuki and Fukushima of Toyota Center R&D Company prepared exfoliated nylon 6/ montmorillonite nanocomposites and polyimide/montmorillonite nanocomposites by in-situ polymerization of caprolactam (quaternary ammonium salt modified montmorillonite was uniformly dispersed in caprolactam in advance). It is found that only 2% (mass fraction) clay is added, and the gas barrier property and linear expansion coefficient of the material are significantly reduced, which is suitable for the application of PI in microelectronics.
R A Vaia and E P Giannelis of Comell University in the United States have made a thermodynamic analysis of polymer melt intercalation, and think that the process is enthalpy-driven, so the interaction between polymer and clay must be strengthened to compensate for the decrease of entropy value of the whole system. Under the guidance of this theory, they prepared PS/ clay and polyoxyethylene/clay nanocomposites through polymer melt intercalation, and studied the confined motion behavior of interlayer polymers. Usuki et al. deeply studied the influence of organic intercalation agent on intercalation compound and prepared a series of PLS nanocomposites. First, they reported that polyamide 6/ montmorillonite nanocomposites were prepared by "two-step method", that is, 12~ 18 alkyl amino acids were used as intercalation agent to exchange cations on sodium-based montmorillonite, and then the cation-exchanged montmorillonite was compounded with ε-caprolactam. Some countries in western Europe have also made plans to develop research on nanocomposites. Some large foreign companies, especially polymer manufacturers, have joined the development and application of polymer nanomaterials.
At present, Toyota Motor Corporation has successfully applied nylon 6/ clay nanocomposites to automobiles. Because layered silicate is dispersed in polymer matrix in nanometer scale, it can be formed into film, blown into bottles and spun. In the process of film forming and bottle blowing, silicate platelets are oriented in the plane to form a barrier layer, so it can be used for high-performance packaging and fresh-keeping film.
2. Research status of 2.PLS nanocomposites in China
The research of PLS nanocomposites in China began in the 1990s, and many achievements have been made, which have been listed in the National "863 Plan" and "Ninth Five-Year Plan". Based on the research of polymer-based clay nanocomposites, Institute of Chemistry, Chinese Academy of Sciences invented a "one-step method" to prepare nylon 6/ clay nanocomposites (nc-PA6), that is, montmorillonite cation exchange, caprolactam monomer intercalation and monomer polymerization were completed in the same dispersion system, which shortened the process flow and reduced the cost without reducing the product performance. Huang Rui's research on modifying polymers with rigid particles has great influence in academic circles. In addition, the preparation of polymer-based nanocomposites by the grinding disc method and ultrasonic method invented by the State Key Laboratory of Polymer Science and Engineering of Sichuan University is also a promising preparation method.
The research results of the State Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences are as follows: The preparation of nylon 6/ clay nanocomposites by monomer intercalation polycondensation can greatly increase its thermal deformation temperature and expand the application range of materials. The relationship between the carbon chain length of intercalation agent and the spacing of organic montmorillonite was studied, and on this basis, PET/ clay and PBT/ clay nanocomposites were developed, which improved the thermal properties and barrier properties of the materials. Among them, crystallization of PET/ clay nanocomposites In addition, silicone rubber/montmorillonite and PS/ clay nanocomposites were prepared by polymer solution intercalation method and melt intercalation method respectively. Among them, silicone rubber/montmorillonite nanocomposites have good wear resistance and various physical and mechanical properties have been greatly improved, which can replace fumed silica to fill silicone rubber and have practical prospects. It is believed that PLS nanocomposites will be widely used in polymer materials and other fields in the near future.
3. Existing problems and research development trend.
With the continuous emergence of PLS nanocomposites and the reports of a large number of research results, we can see the excellent characteristics of such composites, which makes the preparation of high-performance nanocomposites with layered inorganic intercalation modified polymers become one of the latest technical hotspots in the world, but there are also the following problems.
① Although the research of PLS nanocomposites has been very popular, the research of PLS nanocomposites is not deep enough, especially by using the knowledge of thermodynamics, dynamics and crystallography, because of its complex intercalation mechanism, complex structure and interface characteristics, small micro-area size, quantum effect and surface effect. There is little research on the relationship between its structure, morphological characteristics and material properties, and the synthesis methods are mostly based on the improvement of synthetic macro-materials, which has certain limitations;
② The properties of exfoliated PLS nanocomposites are better than other types of composites, but the processing and preparation methods of raw materials are strict, and the research on preparation technology and technology is not enough;
(3) The mixing and dispersion of polymer and nano-materials lacks professional equipment, and traditional equipment can't disperse nano-particles well, so it is necessary to develop new mixing and dispersion technology and equipment.
Third, the content and implementation plan of the subject to be studied
(The main research contents and expected results, the feasibility analysis of the research methods, technical routes and experimental schemes to be adopted. )
1, research content
(1) Understand the physical and chemical properties, synthesis methods, uses and research status of the corresponding polymers; Understand the excellent properties of PLS nanocomposites, and be familiar with the application status, research progress, existing problems and solutions of PLS nanocomposites at home and abroad;
(2) Study the mineralogical characteristics and nanostructure characteristics (interlayer spacing, interlayer characteristics and edge characteristics) of layered silicate (bentonite), and be familiar with the testing and characterization methods; And master the technical methods of analyzing the test results;
(3) Thoroughly study various methods and reaction mechanisms of bentonite purification, sodium and organization; Understand the application value and research status of sodium-based soil and organic soil; Formulate a reasonable experimental scheme, purify bentonite, and select appropriate reaction conditions, sodium agent and surface modifier for sodium and texture through experiments to prepare oleophilic or hydrophilic oleophilic nano-bentonite;
(4) Understand the preparation method and performance characteristics of exfoliated PLS nanocomposites, and discuss the compounding process and mechanism of nanocomposites from the aspects of kinetics, thermodynamics, crystallography and rheology.
(5) Poly (butylene terephthalate) (PBT) and polyurethane (PU) were selected for modification (grafting method and ionization method), a reasonable processing and preparation scheme was worked out, and the best experimental process and parameters were determined to prepare exfoliated PLS nanocomposites;
(6) The dispersion morphology of organobentonite in polymer was studied from the aspects of preparation method, selection of surface modifier and addition of the third component. The structural characteristics of phase interface in multiphase system were discussed, and exfoliated nanocomposites were prepared.
(7) Study the relationship between the structure and properties of PLS nanocomposites. The structural analysis, mechanical properties and flame retardancy of the product were compared and analyzed.
2. Expected results
(1) Preparation of organobentonite and polymer with excellent modification performance;
(2) preparing exfoliated PLS nanocomposites;
(3) It is expected to publish 2 papers in core journals or declare invention patents 1 item;
(4) Finish the graduation thesis and successfully pass the defense.
3. Research methods and technical routes
(1) experimental research flow chart
(2) Experimental research process (scheme)
① Selection and modification of layered silicate
Up to now, bentonite, kaolin, sepiolite and other minerals belonging to layered silicate can be applied to PLS nanocomposites. The most fundamental reason is that most layered inorganic minerals can't enlarge the repeated spacing between layers by intercalation. Therefore, although they have a layered structure with a certain spacing between adjacent layers, they are not enough to accommodate the insertion of polymer molecular chains with a rotation radius of several hundred angstroms between layers, forming so-called intercalation compounds; Only small media such as ions and small molecules are allowed to enter. For clay minerals such as bentonite and kaolin, because of their large initial spacing, interlayer cations can be exchanged, we can use ion exchange to expand their interlayer spacing to the extent that polymer molecular chains can be inserted, thus using them to prepare intercalated nanocomposites with excellent properties.
In this paper, bentonite, the dominant mineral resource in this province, is used, and its main component is montmorillonite. The basic structural unit of montmorillonite is an aluminum-oxygen octahedron sandwiched between two silicon-oxygen tetrahedrons and oxygen atoms, which belongs to 2: 1 layered silicate. Each structural unit is lamellar with the thickness of 1nm and the length and width of 100nm, and there are exchangeable cations between layers, such as metal ions such as Na+, Ca2+ and Mg2+, so it is easy to exchange with alkyl quaternary ammonium salts or other organic cations to generate organobentonite. Due to the poor lipophilicity of bentonite itself, the monomers or molecular chains of polymers are mostly lipophilic substances. Therefore, bentonite must be organically modified before use.
Modification scheme of bentonite.
I. Purification of Bentonite
Experimental scheme: bentonite and water (solid-liquid ratio 1: 10) are mixed to form a suspension, which is then settled and separated by a high-speed rotating centrifuge, and a proper amount of dispersant (sodium hexametaphosphate) is added to further separate fine clastic minerals (feldspar, carbonate, etc.). ), and the particle size is less than 5? Then the suspension is filtered, washed, dried, dispersed and depolymerized to obtain high-purity bentonite products. The blue absorption, CEC, swelling ratio and colloid price were determined.
B, calcium-based bentonite sodium
Sodium principle: when there are two kinds of ions in bentonite-water system, there is a dynamic adsorption-desorption equilibrium, that is, ion adsorption exchange process. For example, when the bentonite-water system contains both Ca2+ and Na+, the following ion exchange equilibrium will occur:
Calcium bentonite +2Na+ 2Na- bentonite +Ca2+
The selection and dosage of sodium agent, sodium temperature and sodium time all have certain effects on the sodium effect. The optimum reaction conditions were determined by experiments.
C. organic bentonite
In the preparation of PLS nanocomposites, organic cations (intercalation agents) are often used for ion exchange, so as to increase the interlayer spacing, improve the interlayer microenvironment, change the inner and outer surfaces of clay from hydrophilic to hydrophobic, and reduce the surface energy of silicate, which is conducive to the insertion of monomers or polymers between clay layers to form PLS nanocomposites. Therefore, the choice of intercalation agent is one of the key steps to prepare PLS nanocomposites. The following conditions must be met: (1) is easy to enter the nano-space between layered silicate wafers (00 1 plane) and can significantly increase the interlayer spacing between clay wafers; (2) The intercalator molecule should have strong physical or chemical interaction with polymer monomer or polymer chain; (3) cheap and easily available, preferably existing industrial products.
Under different dosage, pH, reaction temperature and other conditions. Cation (cetyltrimethyl ammonium bromide), anion (sodium dodecyl sulfate) and anion were selected as intercalation agents to prepare organic soil, and the optimum reaction conditions were determined through experiments.
② polymer modification
Preparation of PLS nanocomposites
I. Types of composite materials
From the microstructure point of view, composite materials can be divided into four categories, as shown in the following figure. In the first composite (a), montmorillonite particles are dispersed in the polymer matrix, but the contact between the polymer and montmorillonite is limited to the surface of montmorillonite particles, and the polymer does not enter the montmorillonite particles. In the second composite (b), the polymer enters the montmorillonite particles, but is not inserted into the silicate lamellae. In the intercalation compound (C), the polymer not only enters the montmorillonite particles, but also intercalates into the silicate lamellae, so that the interlayer spacing of montmorillonite is obviously expanded, but the original direction is still maintained, and the lamellae still have a certain order. In the exfoliated composite (D), the silicate lamellae of montmorillonite are completely disordered and irregularly dispersed in the polymer matrix. At this time, the montmorillonite lamellae and the polymer are uniformly mixed in nanometer scale. Among the four composites, only the latter two can be regarded as nanocomposites, and the fourth exfoliated composite has better properties than the third intercalated composite, which is the goal pursued by many materials scientists and the focus of this study.
B, preparation method
Intercalation composite is a method to prepare PLS nanocomposites. According to the compounding process, intercalation compounding method can be divided into two categories. (1) Intercalation polymerization, that is, polymer monomers are dispersed and intercalated into layered silicate lamellae, and then in-situ polymerization is carried out, and a large amount of heat released in the polymerization process is used to overcome the coulomb force between silicate lamellae, so that the silicate lamellae are peeled off and the polymer matrix is compounded into nanometer scale; (2) Polymer intercalation, that is, mixing polymer melt or solution with layered silicate, peeling layered silicate into nano-scale platelets by mechanochemistry or thermodynamics, and uniformly dispersing them in the polymer matrix.
According to the preparation methods, PLS nanocomposites can be divided into in-situ polymerization of monomer intercalation and direct intercalation of macromolecules. As far as implementation methods are concerned, there are solution methods and fusion methods. They are combined into four specific preparation processes: direct intercalation of polymer melt; Direct intercalation of polymer solution; In-situ bulk polymerization of monomer melt intercalation: and in-situ solution polymerization of monomer solution intercalation. The flow chart for preparing PLS nanocomposites is as follows:
C. Selection of organic soil addition
The amount of organic soil directly affects the quality and performance of products. When the amount of organic soil is too high, the viscosity of the system increases, and it is difficult to defoam and dump. When the amount of organic soil is too low, the dispersibility of organic soil in the system is not good, and the effect of strengthening and toughening can not be achieved. There are different opinions on the amount of organic soil added in the research field. We used different contents (2-5%) of organic soil for intercalation compounding to find the best addition.
D, experimental scheme
Taking PBT and PU polymers as examples, their mechanical properties, flame retardancy and thermal stability were analyzed. It is determined by selecting appropriate intercalation methods and intercalation compounding with different blending ratios. The composite mechanism and factors affecting the composite process were studied from the point of view of thermodynamics and kinetics, and the exfoliated PLS nanocomposites with excellent properties were obtained.
(3) Testing and characterization of the main properties of 3)PLS nanocomposites.
① The cation exchange capacity of bentonite was measured by formaldehyde volumetric method, the content of montmorillonite in bentonite was calculated by blue measurement method, and its expansion multiple and colloid price were measured by measuring cylinder with plug;
② Scanning electron microscope (SEM) was used to measure the micro-morphology of polymer and PLS nanocomposites;
(3) Fourier transform infrared spectroscopy (FTIR) analysis, judging the organic modification effect and intercalation effect according to the absorption peak of the spectrum;
④ X-ray diffraction analyzer (XRD) was used to test the interlayer spacing of bentonite and the peeling degree of the composite; According to the spectrogram, the chemical composition and content of montmorillonite were determined by Jade software.
⑤ The phase transition temperature of bentonite and the thermal stability of the composites were measured by TG-DTA;
⑥ The tensile strength and elongation at break were measured by electronic universal testing machine to judge the mechanical properties of polymer and PLS nanocomposites.
4. Feasibility analysis of experimental research scheme.
(1) The laboratory has a series of experimental instruments, such as vacuum pump, magnetic stirrer, constant temperature water bath pot, high temperature furnace, drying box, opener, twin-screw machine, granulator, etc. The school testing center has scanning electron microscope, X-ray diffractometer, Fourier transform infrared spectrometer, differential thermal-thermogravimetric analyzer, atomic force microscope and other testing instruments.
(2) The tutor has been engaged in research work in this field for a long time, has a solid theoretical foundation and rich practical experience, and has a research team composed of teachers and students;
(3) The school library can find a large number of Chinese and foreign literature and academic monographs for reference;
(4) Cooperation with enterprises has rich practical foundation and broad application prospects;
(5) After some preliminary work, the mechanical properties of the composites are obviously improved and the thermal stability is very good;
(6) The experimental scheme is reasonable, the technical route is feasible, the theoretical basis is clear, and the experimental research conditions are basically available. The progress of the previous research work makes this experimental research scheme feasible.
Fourth, the innovation of research.
What are the innovations in research contents, research methods to be adopted and technical routes? )
As a new research field, (1)PLS nanocomposites, especially exfoliated composites, are still in the primary stage, and the theory and preparation technology are not mature enough. The composite mechanism, structure and the relationship between structure and properties of materials need to be further explored. In this paper, the interfacial characteristics and internal bonding mechanism between polymer and layered silicate (bentonite) are studied from the perspective of thermodynamics and kinetics, and the effects of composite technology and material structure on its mechanical properties, barrier properties, rheological properties and crystallization properties are discussed.
(2) The development level of exfoliated PLS nanocomposites is still in the experimental research or patent stage, and there are few industrialization projects, and there are few research reports on high-performance engineering plastics and high-performance resin matrix. In this paper, the selection of surface modifiers, the addition of the third component, the preparation of high-performance nano-bentonite, the modification of polymers and the selection of reasonable preparation methods were systematically studied to prepare exfoliated nanocomposites with excellent properties.
Verb (abbreviation of verb) workload and work progress (including literature review, scheme design and implementation, calculation and experiment, paper writing, etc. )
Start and end date of project stage work progress
2007.2~2007.9
2007. 10~2007. 12
2008. 1~2008.2
2008.3~2008.4
2008.5~2008.6
2008.7~2008.8
2008.9~2008. 10
2008. 1 1~2008. 12
2009. 1~2009.3
Consult literature, academic monographs, reference books, etc. , and did a lot of preliminary experimental work and some experimental research work;
Write the opening report and defense, and prepare the reagents and instruments needed for the experiment;
Study the structure of sodium-based soil and organic soil and the relationship between structure and performance, and design the experimental scheme; The optimum reaction conditions of sodium method and organic method were determined through experiments and performance characterization. A large number of organic soils were prepared under the optimum reaction conditions, characterized by XRD, FTIR and TG-DTA, and the experimental records were made.
Taking PBT and PU polymers as examples, the physical and chemical properties, synthesis mechanism, synthesis methods and application status are understood. Select the appropriate reaction device and synthesis method to synthesize the required polymer with the monomer;
Consult a large number of latest Chinese and foreign literatures to understand the research status and advanced preparation methods of nanocomposites; PLS nanocomposites were prepared by different methods, such as polymer melt intercalation, polymer melt intercalation and monomer insertion in-situ polymerization, with different organic soil addition (2-5%).
The mechanical properties, thermal properties and barrier properties of the product were tested, the optimum amount of organic soil was determined, and the environmentally friendly preparation method was found out even if the product had excellent performance and low cost.
The morphology of the product was tested by SEM to determine the peeling degree. The interlayer spacing of organic soil was tested by XRD, and its modification effect was analyzed. The properties of the interface layer in composites can be characterized by differential scanning calorimetry (DSC). Thermogravimetric analysis can be used to study the modification degree of montmorillonite by organic matter and the heat resistance of nanocomposites.
Select the best preparation method, compound polymer with organic soil, develop nano-composite products and characterize their properties in detail;
Write a thesis and prepare a defense.
Six, the main references at home and abroad (list the author, the name of the paper, the name of the journal, the year of publication).
Serial number reference name
Liang Hongbin, Ni Jingbin. Research progress of polymer/nanocomposites [J]. Chemical Engineer, 2006, 3: 26-28.
Chen Guangming, Li Qiang and Qi Zongneng. Research progress of polymer/layered silicate nanocomposites [J]. Polymer Bulletin,1999,4:1-9.
Han Jianzhu, Xia Ying. Research progress of polymer/montmorillonite nanocomposites [J]. Polymer Bulletin, 2006, 12: 66-70.
Li Chunsheng, Chunhui Zhou and Li. Research progress of polymer/montmorillonite nanocomposites [J]. Chemical Production Technology, 2002,9 (4): 22-26.
Chen Guohua, Li Mingchun. Polymer/Clay Nanosystem [J]. Polymer Materials Science and Engineering, 1999, 15 (3): 9- 12.
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Shu, Qi Zongneng. Polymer/clay nanocomposites and their special flame retardant properties [J] .2000,28 (3): 24-26.
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Zhou, Lu Anhuai. Experimental study on preparation of low-cost organoclay from low-grade natural calcium-based bentonite [J]. Journal of Peking University (Natural Science Edition), 2006,42 (4) 457-467.
Chen Xinghua. The latest research progress of polymer/layered silicate nanocomposites [J]. Guangxi Light Industry, 2007, (1): 35-37.
Rui Huang, Wang Xu, Li Zhongming. Development, application and progress of nano plastic polymer/nano inorganic composite [J]. China Light Industry Press, 2002, (4): 10- 12.
Zhu Qiru, Huang Zhiliang, Wang Xiwen, et al. Combined treatment process of bentonite purification, whitening and sodium modification [J]. China Mining, 2002, 1 1 (5): 44-46.
Qi Zongneng, Shang Wen. Theory and Practice of Polymer/Layered Silicate Nanocomposites [M]. Chemical Industry Press, 2002.
Synthesis and characterization of novel multiblock polyurethane/clay nanocomposites. Polymer, 2000,41(4):1345-1349.
Zhao, Li, Quan, Applied Polymer Science 200 1, (79): 1025- 1028.
G-M.Kim D-H，Lee，B.Hofmann，et a 1。 Effect of nano-fillers on the deformation process of layered silicate/polyamide-12 nanocomposites. Polymer, 200 1, 42(3):95- 1 10.
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Tianan Second Park, Park, etc. a 1. Polymer.200 1，42:7465-7475。
Fornes T D，Yoo P J，et a 1。 Polymer.200 1，42:9929-9940。
Polymer, 200 1, 42: 1083- 1094.
Kanfei Toman R.el a 1. Polymer 2002.43:2909-29 16.
Dennis H R, hunter D L, a 1. Polymer .2001,42:95 13-9522.
Wang Xiaoming, Wang Xiaoming, etc. Fire and polymers, 2006, 4:2005.
Sorathia U, Lynon R, Gann R G. Fire fighting technology,1997,33 (3): 351.
South S.R.ay, K.YamadaM, Okamoto, et a 1. Novel polylactic acid-layered silicate nanocomposites.
Improvement of material properties, biodegradability and melt rheology [J]. Polymer, 2003.44(3):857-866.
Wang, Wang, et al. Preparation and properties of polypropylene/montmorillonite nanocomposites [J]. Modern plastics processing and application, 2005,17 (2):14-16.
Sue, Zeng. Preparation and Conductivity of Polypyrrole/Organomontmorillonite Nanocomposites [J]. Chemistry and Bonding, 2005,27 (3):127-130.
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Wu Defeng, Zhou Zhixing. Crystal structure and rheological behavior of polybutylene terephthalate/montmorillonite nanocomposites [J]. Polymer Materials and Engineering, 2005,21(5):132-136.
1, listing at least 20 references at home and abroad;
2. Textbooks and reference books cannot be used as reference;
3. The number of reference books such as monographs is less than one third of the total;
4, the number of reference books published in recent five years is not less than one-third of the total;
5, the number of foreign language references is not less than one-third of the total.