This licentiate thesis is devoted to the investigation of how bonding in simple organic molecules are affected by X-ray beam irradiation. The investigation targets molecules with three carbons as their main-chain structure. The stability of the bonds under ionization are simulated using the SIESTA package. SIESTA is a simulation package that provides molecular dynamics simulations based on density functional theory within the Born-Oppenheimer approximation. The aim of this study is to understand statistically the damaging process and selectivity among different types of bond. As the first targets, 4 hydrocarbons are investigated. They are propane, propene, propyne and propadiene, which have different combinations of single, double and triple bonds as their main-chain structures. Depending on the combinations, the structures can be either symmetric around the central atom or not. The structure of the symmetric molecules propane and propadiene are  stable until charge +3. In contrast, the asymmetric molecules propene and propyne, the  main-chain bonds show a tendency towards a more similar bond-distance as the level of ionization increases. In addition, hydrogens relocation occurs in propene, leading to a symmetric structure. Secondly, the bond fluctuations are investigated among 4 types of three-carbon molecules which have functional parts. Alcohol and carboxyl groups molecules show the stable bond integrities at charging 0 to +2. On the other hand, the carbon-carbon bonds in molecules with  acetyl and ketone groups are broken by ionization. Comparing the 8 kinds of bond breaking processes in these molecules, this statistical study gives an insight to organic molecules bonding systems.

This body of research investigated the bonding efficiency of self-etching primer adhesives to enamel and dentine with various surface characteristics. A series of preliminary experiments was carried out to determine the effect of operator experience, dentine tubule orientation, bond strength test method and resin composite material used on bond strengths. The results of the preliminary tests concluded that it is essential to develop skills in material handling and the test methods used; 2-step self-etching primer adhesives exhibit higher but more variable microshear bond strengths (µSBS) than ‘all-in-one’ adhesives on dentine at different depths and tubule orientations; fracture toughness and bond strength test results suggest that the fracture toughness of a resin composite may not be of significant influence on microtensile and µSBS tests outcomes for nano-filled hybrid materials. / An investigation of the bonding ability of self-etching primer adhesives under various tooth preparation conditions was carried out. Enamel and dentine specimens were prepared from human teeth and finished with various rotary cutting instruments and the erbium, chromium:yttrium, scandium, gallium, garnet laser. Specimens were bonded with two 2-step self-etching primer adhesives and two ‘all-in-one’ adhesives with a resin composite. The results showed that one of the 2-step adhesives exhibited higher but more variable µSBS than the ‘all-in-one’ adhesives and a silorane-based self-etching primer adhesive system to enamel and dentine. / The relationship between enamel microhardness and µSBS was evaluated. Enamel specimens were prepared and finished with one half of the surface tested for hardness using the Vickers test. The other half of the enamel surface was bonded using either a 2-step self-etching primer adhesive or an ‘all-in-one’ adhesive and a hybrid resin composite. Mean Vickers hardness numbers and µSBS for each enamel surface were calculated. Analysis using Pearson’s parametric test for regression analysis evaluated the correlation between Vickers hardness and µSBS. The results revealed a weak negative insignificant correlation between VHN and µSBS for the 2-step adhesive and no correlation for the ‘all-in-one’ adhesive. / The effect of conditioning and casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) on bonding to bleached and unbleached enamel was investigated. Four groups of enamel specimens: untreated control; bleaching with 16% carbamide peroxide gel for 90 min daily x 14 days; treated with CPP-ACP paste (Tooth Mousse, GC Corp., Japan) for 60 min daily x 7 days and bleached and CPP-ACP-treated were used. The specimens were divided into a further two groups and bonded with a total-etch adhesive or a 2-step self-etching primer adhesive. Specimens bonded with the self-etching primer adhesive were sub-divided into four conditioning subgroups before bonding: no conditioning; 30 – 40% phosphoric; 15% EDTA; 20% polyacrylic acid. Specimens were tested in shear mode until failure and analysed by 2-way ANOVA, one-way ANOVA and Tukey’s post-hoc test. The µSBS of the total-etch adhesive was not affected by enamel treatment. Bleaching reduced the µSBS of the self-etching primer adhesive but preconditioning with phosphoric acid and polyacrylic acid improved bond strengths after CPP-ACP application. Bond failure analysis revealed a predominance of adhesive failures after bleaching, but prior conditioning reduced the proportion of adhesive failures. Scanning electron microscopy (SEM) revealed that the interfacial morphology produced by the 2-step self-etching primer adhesive was independent of enamel treatment except after bleaching. Phosphoric acid etching was not inhibited by CPP-ACP treatment. Resin tag formation was observed with prior phosphoric acid and polyacrylic acid conditioning. / The effect of conditioning and CPP-ACP application on dentine bonding was also investigated. Dentine specimens with and without the smear layer were prepared and divided into a further two groups, CPP-ACP paste applied to one group for 60 min daily x 7 days and the other group was untreated. The two groups were divided into three subgroups for conditioning: no conditioning; 30 - 40% phosphoric acid; 20% polyacrylic acid. The dentine was bonded using a 2-step self-etching primer adhesive and an ‘all-in-one’ adhesive, and tested as previously described. Statistical analysis was carried out using one-way ANOVA and Tukey’s post-hoc test at α = 0.05. The results showed that the µSBS of both adhesives were not significantly affected on smear-covered dentine but was affected on smearless dentine. Conditioning did not improve bond strengths. Bond failure analysis showed more adhesive failures for the ‘all-in-one’ adhesive, particularly on smearless dentine and with prior polyacrylic acid conditioning. SEM revealed a similar morphology of the bonded interface for the 2-step self-etching primer adhesive regardless of conditioning; and areas of bond failures for the ‘all-in-one’ adhesive. / The 2-step self-etching primer adhesives exhibited higher bond strength and more regular bond integrity than the ‘all-in-one’ adhesives, as shown on the SEM observations. However, the ‘all-in-one’ adhesives exhibited less variability in bond strengths to tooth surface characteristics.

Adhesive bonding which has been in use for long as a traditional joining method has gained ground in the last couple of decades due to the introduction of advanced composite materials into the aerospace industry. Bonded structures have advantages such as high corrosion and fatigue resistance, ability to join dissimilar materials, reduced stress concentration, uniform stress distribution, good damping characteristics etc. They also have certain limitations like environmental degradation, existence of defects like pores, voids and disbonds, difficulty in maintenance and repair etc. A serious drawback in the use of adhesively bonded structures has been that there are no established comprehensive non-destructive testing (NDT) techniques for their evaluation. Further, a reliable evaluation of the effect of the existing defects on strength and durability of adhesive joints is yet to be achieved. This has been a challenge for the research and development community over several decades and hence, been the motivation behind this piece of research work. Under the scope of the work carried out in the thesis, some of the primary factors such as the existence of defects, degradation of the adhesive, stress and strain distribution in the bonded region etc., have been considered to study the bond integrity in composite to composite lap shear joints. The problem becomes complex if all the parameters affecting the adhesive joint are varied simultaneously. Taking this into consideration, one of the key parameters affecting the bond quality, viz., the adhesive layer degradation was chosen to study its effect on the bonded joint. The epoxy layer was added with different, definite amount of Poly vinyl alcohol (PVA) to arrive at sets of bonded joint specimens with varied adhesive layer properties. A thorough review of different non destructive testing methods applied to this particular problem showed that ultrasonic wave based techniques could be the right choice. To start with, preliminary experimental investigations were carried on unidirectional glass fiber reinforced plastic (GFRP-epoxy) lap joints. The adhesive joints were subjected to non destructive evaluation (NDE) using ultrasonic through transmission and pulse echo techniques as also low energy digital X-ray techniques. The results obtained showed a variation in reflected and transmitted ultrasonic pulse amplitude with bond quality. Digital X-Ray radiography technique showed a variation in the intensity of transmitted x-rays due to variation in the density of adhesive. Standard mechanical tests revealed that the addition of PVA decreased the bond strength. A plot of coefficient of reflection from the first interface and the bond strength showed a linear correlation between them. After obtaining a cursory feel and understanding of the parameters involved with the preliminary experiments on GFRP adhesive joints which yielded interesting and encouraging results, further work was carried on specimens made out of autoclave cured carbon fiber reinforced plastic (CFRP)-epoxy bonded joints. Normal incidence ultrasound showed a similar trend. Analyses of the Acoustic Emission (AE) signals generated indicate early AE activity for degraded joints compared to healthy joints. Literary evidences suggest that the ultrasonic shear waves are more sensitive to interfacial degradation. An attempt was made to use oblique incidence ultrasonic interrogation using shear waves. The amplitude of reflected shear waves from the interface increased with an increase in degradation. Further, a signal analysis approach in the frequency domain revealed a shift in the frequency minimum towards lower range in degraded samples. This phenomenon was verified using analytical models. An inversion algorithm was used to determine the interfacial transverse stiffness which decreased significantly due to increase in degradation. Conventional ultrasonic evaluation methods are rendered ineffective when a direct access to the test region is not possible; a different approach with guided wave techniques can be explored in this scenario. Investigations on CFRP-epoxy adhesive joints using Lamb waves showed a decrease in the amplitude of ‘So’ mode in degraded samples. Theoretical dispersion curves exhibited a similar trend. Frequency domain studies on the received modes using Gabor wavelet transform showed a negative shift in frequency with increased degradation. It was also observed that the maximum transmission loss for the most degraded sample with 40 percent PVA occurred in the range of 650 – 800 kHz. Non linear ultrasonic (NLU) evaluation revealed that the nonlinearity parameter (β) increased with increased degradation. Kissing bonds are most commonly occurring type of defects in adhesive joints and are very difficult to characterize. A recent non-contact imaging technique called digital image correlation (DIC) was tried to evaluate composite adhesive joints with varied percentage of inserted kissing bond defects. The results obtained indicate that DIC can detect the kissing bonds even at 50 percent of the failure load. In addition, to different experimental approaches to evaluate the bonded joint discussed above, the effect of degradation on the stresses in the bond line region was studied using analytical and numerical approach. A linear adhesive beam model based on Euler beam theory and a nonlinear adhesive beam model based on Timoshenko beam theory were used to determine the adhesive peel and shear stress in the joint. Digital image correlation technique was used to experimentally obtain the bond line strains and corresponding stresses were computed assuming a plane strain condition. It was found that the experimental stresses followed a similar trend to that predicted by the two analytical models. A maximum peel stress failure criterion was used to predict failure loads. A failure mechanism was proposed based on the observations made during the experimental work. It was further shown that the critical strain energy release rate for crack initiation in a healthy joint is much higher compared to a degraded joint. The analytical models become cumbersome if a larger number of factors have to be taken into account. Numerical methods like finite element analysis are found to be promising in overcoming these hurdles. Numerical investigation using 3D finite element analysis was carried out on CFRP-epoxy adhesive joints. The adherend – adhesive interface was modeled using connector elements whose stiffness properties as well as the bulk adhesive properties for joints with different amounts of PVA were determined using ultrasonic inspection method. The peel and shear stress variation along the adhesive bond line showed a similar trend as observed with the experimental stress distribution (DIC) but with a lesser magnitude. A parametric study using finite element based Monte-Carlo simulation was carried out to assess the effect of variation in various joint parameters like adhesive modulus, bondline thickness, adherend geometrical and material properties on peel and shear stress in the joint. It was found that the adhesive modulus and bond line thickness had a significant influence on the magnitude of stresses developed in the bond line. Thus, to summarize, an attempt has been made to study the bond line integrity of a composite epoxy adhesive lap joint using experimental, analytical and numerical approaches. Advanced NDE tools like oblique incidence ultrasound, non linear ultrasound, Lamb wave inspection and digital image correlation have been used to extract parameters which can be used to evaluate composite bonded joints. The results obtained and reported in the thesis have been encouraging and indicate that in specific cases where the bond line thickness and other relevant parameters if can be maintained or presumed reasonably non variant, it is possible to effectively evaluate the integrity of a composite bonded joint.