Apparent volumetric shrinkage study of RTM6 resin during the curing process and its effect on the residual stresses in a composite

A comprehensive characterization of the volumetric shrinkage of a commercially important aerospace resin (RTM6) during the various stages of the curing process was studied. The apparent volumetric shrinkage, evaluated from density measurements at room temperature, was correlated with the progress of epoxide conversion. During the entire curing process, the apparent volume shrinkage was found to be less than 3% and occurred before vitrification. A slight re‐expansion of the resin, attributed to self‐antiplasticization effects, was observed during postcuring at 180°C. It was concluded that residual stresses were not generated due to chemical cross‐linking during curing but rather from thermal contraction occurring during the cooling stage after cure. A photo‐elastic method was used to characterize residual stresses during cooling in a deliberately engineered resin rich hole of a carbon fiber/RTM6 composite. The residual stress was found to reach approximately 28 MPa, which is in good agreement with the value calculated from the shrinkage and elastic moduli. It is proposed that this simple method can be provide insights useful to the design and materials selection processes by measuring and localizing residual stresses from resin during curing and or thermal cycling. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Stress‐initiated void formation during cure of a three‐dimensionally constrained thermoset resin

During cure of epoxy resins, polymerization induces an increase in mechanical properties, which is accompanied by a volumetric shrinkage. When the resin is cured in a constrained mold to which it adheres, tensile stresses will hence develop, which may exceed the stremgth of the resin at a given curing stage. Voids will then form. The origin and governing parameters of void formation are studied using an epoxy resin cured in a three‐dimensionally constrained glass mold following isothermal cure cycles. Two types of voids are shown to appear during cure, one early in the process and a second around the gelation point. A viscoelastic analysis of the material stress state over the whole range of cure is performed. Both the viscoelastic modulus obtained from a time‐cure‐temperature superposition and the volumetric shrinkage, which was continuously measured by density change, are taken into account. A value for the critical internal stress at void initiation is thus proposed. This criterion can be used to provide guidelines for tailoring the material properties toward an increase of the critical stress for void initiation. Also, since during theprocessing of composite materials, cases may arise where the resin cures within the interstices left between consolidated fibres that do not move, this critical stress failure criterion can be of use in the eastablishment of a process window providing guidelines for the production of void free composites.     

Study on the volumetric expansion of benzoxazine curing with different catalysts

A systematic investigation on the volumetric expansion of four benzoxazine systems, which are benzoxazine, benzoxazine/tertiary amine, benzoxazine/organic acid, and benzoxazine/epoxy resin/tertiary amine, was done. By using gravitometric and dilatometric methods, etc., studies on volumetric shrinkage, isothermal cure shrinkage, and density versus cure time plots were done. The cure reactions of these benzoxazines were carried out at 140 and 160°C. The results show that all benzoxazine systems exhibit apparent volumetric expansion after polymerization, that is, the densities of monomers are larger than are those of polymers at room temperature. But, meanwhile, they exhibit volumetric shrinkage while curing isothermally. The results also show that the higher the cure temperature is, the larger the cure shrinkage of the benzoxazines will be and that the extent of the cure shrinkage of the benzoxazines with the aid of catalysts is larger than is that of thermal polymerization systems. The reason for this is that, accelerated by catalysts, the polymerization rate become faster and the extent of polymerizatiom becomes larger. It is obvious that catalysts can make a notable impact on the cure reaction of benzoxazines. Therefore, the dimension of the volumetric expansion of benzoxazine is associated with its polymerization mechanism, molecular structure, and extent of polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1107–1113, 2002; DOI 10.1002/app.10267     

Polymerization shrinkage,stress, and degree of conversion in silorane‐ and dimethacrylate‐based dental composites

To compare two kind of resin‐based dental composites, the polymerization shrinkage, contraction stress (CS), and degree of conversion (DC) of four dimethacrylate‐based and one silorane‐based composite were investigated. To determine shrinkage, the composites were packed, respectively, into a cylindrical cavity in human teeth and imaged using X‐ray microcomputed tomography to determine the precise volume before and 30 min after photopolymerization. To determine CS, the sample was applied in a similarly sized cylinder in a universal testing machine and monitored for 30 min. FTIR spectroscopy was used to determine DC. The volumetric shrinkage (range: 1.1–3.1%) and maximum CS (range: 1.2–3.5 MPa) differed significantly among the tested composites but not the final DC (range: 62.3–69.1%). The silorane‐based composite displayed the lowest volumetric shrinkage and CS of all composites. No correlation was observed between the stress and volumetric shrinkage values of the dimethacrylate‐based composites. A moderate correlation was found between stress and DC (r = 0.836), which was significant at 20 and 40 s. The silorane‐based composite exhibited superior shrinkage behavior compared with conventional dimethacrylate composites with comparable polymerization kinetics. The CS was dependent on multiple variables, including the volumetric shrinkage, DC, and curing rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In situ monitoring of residual strain development during composite cure

Internal (residual) stresses build up in a thermosetting composite as the matrix shrinks during cure, and again as the composite is cooled to ambient from its elevated processing temperature. These stresses can be significant enough to distort the dimensions and shape of a cured part as well as initiate damage in off‐axis plies, either during fabrication or under the application of relatively low mechanical loads. The magnitude of these stresses depends on a number of factors including constituent anisotropy, volume fraction and thermal expansion, ply orientation, process cycle, and matrix cure chemistry. In this study, embedded strain gauges were employed to follow, in situ, the buildup of residual strains in carbon fiber‐reinforced laminates during cure. The data were compared to those from volumetric dilatometer studies to ascertain the fraction of resin shrinkage that contributed to residual stress buildup during cure. Based on earlier studies with single‐fiber model composites, the process cycle in each case was then varied to determine if the cycles optimized to minimize residual stresses for isolated fibers in an infinite matrix were applicable to the reduction of residual stresses in conventional multifiber composites. The results of these studies are reported here.     

Cure-volume-temperature relationships of epoxy resin and graphite/epoxy composites

Taking the material thermal expansion and curing shrinkage in polymer composites into account, this work aims to quantitatively obtain the relationships among the degree of cure, the volumetric change rate and the temperature (CVT) at the atmospheric pressure. According to reaction kinetics and nonlinear deformation theory, the mathematical models are established to implicitly describe the CVT relationships of epoxy resin as well as its unidirectional graphite fiber composites, and then the volumetric change rates of the two types of materials during curing process are obtained via the finite element method. On the basis of the numerical analysis and data fitting, two new explicit CVT expressions are constructed. The numerical analysis of the cure-volume-temperature relationships is helpful not only for the prediction of material warpage and internal stress, but also for the process optimization, such as the shrinkage compensation of polymer composites. By comparing the present results with the results in published articles, the validity of the present results is proven indirectly.     

固化工艺规范对复合材料固化残余应力影响的实验研究

单束纤维拉伸法是以简单的单束纤维聚合物基复合材料结构为研究对象,研究固化工艺过程中树脂体积变化与纤维上残余应力之间的关系.同时固化过程中树脂体积是随工艺温度变化而产生变化的,经理论分析及计算得到了固化工艺温度历程对纤维上固化残余应力的影响规律.     

Relation between volumetric changes of unsaturated polyester resin and surface finish quality of fiberglass/unsaturated polyester composite panels

Resin dimensional changes, including cure shrinkage and thermal expansion, highly influence the surface finish quality of composite parts. Low profile additives (LPA) are commonly incorporated in unsaturated polyester (UP) resins to compensate for resin shrinkage and obtain a high quality surface finish. In this study, the dimensional change of an UP resin with different LPA contents was characterized. Both resin cure shrinkage and resin thermal expansion were measured. A simple methodology was then developed to estimate the surface finish quality of panels, manufactured by resin transfer molding (RTM), based on the prediction of part thickness variation during the process. Results show good agreement with the experimental investigations. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Multiphysics simulations of cure residual stresses and springback in a thermoset resin using a viscoelastic model with cure‐temperature‐time superposition

Simulations of evolution of cure‐induced stresses in a viscoelastic thermoset resin are presented. The phenomenology involves evolution of resin modulus with degree of cure and temperature, the development of stresses due to crosslink induced shrinkage, and the viscoelastic relaxation of these stresses. For the simulations, the detailed kinetic and chemo‐thermo‐rheological models for an epoxy‐amine thermoset resin system, described in Eom et al. (Polym. Eng. Sci. 2000, 40, 1281) are employed. The implementation of this model into the simulation is facilitated by multiphysics simulation strategies. The trends in simulated cure‐induced stresses obtained using the full‐fledged viscoelastic model are compared with those obtained from two other equivalent material models, one involving a constant elastic modulus, and the other involving a cure‐dependent (but time‐invariant) elastic modulus. It is observed that the viscoelastic model not only results in lower estimates of cure‐induced stresses, but also provides subtle details of the springback behavior. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymerization shrinkage/stress and dentin bond strength of silorane and dimethacrylate‐based dental composites

This study was designed to determine whether a new dedicated adhesive system using a silorane composite exhibits better bonding performance to human dentin than conventional dimethacrylate‐based composites. The materials were used included: Adper? Easy Bond‐Z250 (AE‐Z250), iBond‐Venus (IB‐VE), XenoIII‐TPH (XE‐TPH), Clearfil S3‐Clearfil Majesty (S3‐CM), and the Filtek silorane system (SA‐FS). Polymerization volumetric shrinkage and stress development were measured using a micro‐CT instrument and universal testing machine. The push out strength of the bonds produced using the corresponding self‐etching adhesive systems were also measured. The volumetric shrinkage of the resin composite/adhesive combinations ranged from 1.05% (SA‐FS) to 3.38% (XE‐TPH) 30 min after light curing. SA‐FS had the lowest volumetric shrinkage (P < 0.05), followed by S3‐CM, EA‐Z250, IB‐VE, and XE‐TPH. The polymerization stress of the materials ranged from 1.54 (SA‐FS) to 3.49 MPa (S3‐CM). The lowest stress was also observed in SA‐FS at 30 min during the stress test (P < 0.05). Push‐out bond strength testing revealed that IB‐VE had significantly lower bond strength than other combinations (P < 0.05). The silorane composite and dedicated adhesive system exhibited excellent characteristics of low volumetric shrinkage and stress development compared to conventional dimethacrylate‐based composites. However, the silorane composite resin system possessed similar push‐out bond strength as the other materials, with the exception of the Venus/iBond combination. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Chemorheology of thermosetting resins. III. Effect of low-profile additive on the chemorheology and curing kinetics of unsaturated polyester resin

An experimental study was conducted to investigate the effect of low-profile thermoplastic additives on the rheological behavior during cure and the curing kinetics of unsaturated polyester resin. For the study, a general-purpose polyester resin was used and two different types of thermoplastic additive, poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA), were used as low-profile additives. It has been found that, during cure, the resin/PMMA system exhibits shearthinning behavior even before the cure time reaches the critical value tη∞ whereas the resin/PVAc system does not. Also, both PVAc and PMMA help reduce the shrinkage of the resin during cure. However, our study shows that shrinkage control becomes effective only when the shear rate is greater than a certain critical value. The curing behavior determined with the aid of differential scanning calorimetry (DSC) shows that the rate of cure and the final degree of cure are decreased when the amount of low-profile additive is increased.     

Cure kinetics modeling and cure shrinkage behavior of a thermosetting composite

In this work, the cure kinetics and through‐the‐thickness cure shrinkage upon curing of a carbon fiber‐epoxy composite (AS4/8552) were studied. The study is composed of two major parts. Firstly, dynamic and isothermal Differential Scanning Calorimeter (DSC) scans were performed to develop a new cure kinetics model. The most appropriate kinetic model that produces a nearly perfect fit of all data sets corresponds to a process with two single‐step parallel autocatalytic reactions with diffusion control. Multivariate kinetic analysis was used to evaluate the parameters. In the second part of the study, the coefficients of thermal expansion (CTEs), the glass transition temperatures (T_g), and the through‐the‐thickness cure shrinkage strain values of the partially cured unidirectional and cross‐ply composite samples were measured by using a dynamic mechanical analyzer (DMA). Cure strains were measured throughout the Manufacturer's Recommended Cure Cycle (MRCC) with the same method. Results indicate that glass transition temperatures of partially cured samples can be measured very closely by the two methods (DSC and DMA). The methods proposed were proved to be very reliable to predict the degree of cure and to measure the through‐the‐thickness strains during the cure cycle. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

超支化聚酯的改性及其在牙科修复树脂中的应用

以季戊四醇(B4单体)为核,2,2-二羟甲基丙酸(AB2单体)为单体,对甲苯磺酸为催化剂,通过熔融缩聚反应合成末端为16个羟基的二代Boltorn型超支化聚酯HBP。并进一步用甲基丙烯酰氯、丙酰氯对端羟基进行改性,在HBP末端全部引入双键或部分引入双键,得改性后超支化聚酯GHBP1和GHBP2。在传统牙科修复树脂双酚A甲基丙烯酸缩水甘油酯(Bis-GMA)和二甲基丙烯酸三甘醇酯(TEGDMA)的混合体系中引入不同质量分数的GHBP,考察其对树脂收缩率和双键转化率的影响。结果表明,GHBP改性牙科修复树脂后,树脂的聚合收缩明显降低,且GHBP2具有更优异的减小收缩的性能,但双键转化率无明显变化。     

Internal stress control in epoxy resins and their composites by material and process tailoring

The development of internal stress during cure of epoxy and hyperbranched polymer-modified epoxy resins was characterized, taking into account the evolving viscoelastic properties, the volumetric shrinkage due to the chemical reaction, and the thermal expansion. A criterion for void formation during cure in a constrained mold was proposed, providing guidelines for the construction of a process window for manufacturing of void-free composites. It was shown that the internal stress development in epoxy resins during cure is strongly influenced by the presence of hyperbranched polymer modifiers. The role of these modifiers was illustrated for the case of autoclave processing of glass fiber/epoxy composites. This study showed that higher fiber volume fractions could be used with hyperbranched polymer-modified resins than with unmodified resins, for producing void-free laminates. It also appeared that by suitable tailoring of the process cycle, a fully stress-free laminate could be obtained after cure, using the modified resin.     

Nature of contact between polymer and mold in injection molding. Part II: Influence of mold deflection on pressure history and shrinkage

In injection molding of thermoplastic parts, high hold pressures are set during the packing phase to generate a post‐filling, which compensates the shrinkage of polymer due to its cooling. The polymer pressure in mold cavity leads to a cavity deformation due to mold and machine compliance. Then, the increase in cavity thickness can modify the post‐filling and consequently the pressure history, the volumetric shrinkage and the part mass. The first goal of this paper is to present a simple method to locally determine mold rigidities: over‐packed slabs are injected and local deflections are determined from measurements of the local residual pressure, the local in‐plane shrinkages and the plate thickness. In the studied plate mold, which can be considered as stiff compared to some industrial molds, a rigidity of more than 1 μm/MPa has been measured close to the center of the plate. The second goal of this paper is to show the influence of mold deflection on dimensional properties. If the cavity thickness is small as for our 1‐mm‐thick plate mold, considering an infinitely rigid mold cannot do realistic predictions of polymer pressure history, volumetric shrinkages and part mass. Nevertheless, in‐plane shrinkage seems to be less affected by mold deflection. It means that the additional polymer mass due to mold deflection is mainly distributed in the part thickness.     

Cure shrinkage analysis of epoxy molding compound

EGA (ball grid array), one of the structures Used for semiconductor packages, involves a laminated structure. BGA inevitably involves significant warpage, owing to differences in shrinkage among constituent materials. The extent of warpage is governed by total shrinkage (= cure shrinkage + thermal shrinkage) of the epoxy molding compound that encapsulates the IC chip. In particular, the cure shrinkage exerts great influence on warpage. Cure shrinkage has been understood as the decrease in free volume at the time of curing. However, the cure shrinkage rate cannot be sufficiently explained by the free volume of the cured epoxy resin. We have developed an evaluation method based on the epoxy group reaction ratio, and have eventually confirmed that cure shrinkage depends on the reaction ratio of the epoxy group after curing, and on epoxy group density.     

On‐line mixing during injection and simultaneous curing in liquid composite molding processes

Liquid composite molding (LCM) processes such as resin transfer molding (RTM) and vacuum assisted RTM (VARTM) are used to manufacture high quality and net‐shape fiber reinforced composite parts. All LCM processes impregnate fiber preforms packed in a mold cavity with a thermoset resin. After the preform is fully saturated, the injection is discontinued but the resin continues to cure. Once the curing step is complete, the part is de‐molded. The resin has to be mixed with a curing agent to cure. Typically, the resin and the curing agent are mixed together in a pressure pot before the injection. This has several disadvantages, such as storage of large amounts of hazardous polymerizing resin, wastage, and cleaning of cured resin from the injection line. This paper proposes the implementation and calibration of an alternative to this technique. The approach is to mix the curing agent with the resin as the resin enters the mold through a separate system featuring two feed‐lines. Such a system will enable one to maintain a uniform gel time throughout the part by varying the mixing ratio of resin and the catalyst during the injection. An experimental study of such on‐line mixing to obtain simultaneous curing and to reduce the overall curing time is conducted and presented in this paper. Implementation of a control scheme that varies the curing agent during injection and its effect on cure time is benchmarked with the process in which the percentage of curing agent is held constant. The gel time for the fabricated parts was reduced by 20–25% by continuously varying the percentage of curing agent during injection. POLYM. COMPOS., 26:74–83, 2005. © 2004 Society of Plastics Engineers     

高光注射成型工艺特性研究：翘曲、收缩与沉降指数

以LCD电视机前面壳为例,以高光注射成型制品主要表观品质因素（翘曲变形、沉降指数和体积收缩率）为成型性能指标,利用田口实验法、数值模拟及数据处理技术,对高光注射成型工艺特性进行研究。结果表明,转保压力对产品成型翘曲变形具有决定性的影响,而注射压力和保压压力则对沉降指数和体积收缩率影响显著。进一步研究表明,随着转保压力的逐步增加,产品成型翘曲变形值几乎呈线形下降趋势,当减小至一峰值(1.187 mm)之后,若转保压力继续增加,翘曲变形量会有所增大;产品表面沉降指数和体积收缩率均随注射压力和保压压力的升高而减小,当注射压力升高至一定值(90 MPa)之后,继续增加注射压力对二者的影响将不再显著,而产品表面沉降指数和体积收缩率始终随保压压力的升高呈准线形下降趋势。     

Simulation of injection–compression‐molding process. II. Influence of process characteristics on part shrinkage

A numerical algorithm is developed to simulate the injection–compression molding (ICM) process. A Hele–Shaw fluid‐flow model combined with a modified control‐volume/finite‐element method is implemented to predict the melt‐front advancement and the distributions of pressure, temperature, and flow velocity dynamically during the injection melt filling, compression melt filling, and postfilling stages of the entire process. Part volumetric shrinkage was then investigated by tracing the thermal–mechanical history of the polymer melt via a path display in the pressure–volume–temperature (PVT) diagram during the entire process. Influence of the process parameters including compression speed, switch time from injection to compression, compression stroke, and part thickness on part shrinkage were understood through simulations of a disk part. The simulated results were also compared with those required by conventional injection molding (CIM). It was found that ICM not only shows a significant effect on reducing part shrinkage but also provides much more uniform shrinkage within the whole part as compared with CIM. Although using a higher switch time, lower compression speed, and higher compression stroke may result in a lower molding pressure, however, they do not show an apparent effect on part shrinkage once the compression pressure is the same in the compression‐holding stage. However, using a lower switch time, higher compression speed, and lower compression stroke under the same compression pressure in the postfilling stage will result in an improvement in shrinkage reduction due to the melt‐temperature effect introduced in the end of the filling stage. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1640–1654, 2000