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The free radical addition of saturated polymers and small molecules to unsaturated monomers is used to prepare functional derivatives under solvent-free, reactive extrusion conditions. Of particular interest are the dynamics and yields of conventional peroxide-initiated grafting of vinyltrialkoxysilanes to polyethylene, as well as the mechanisms through which bicumene initiates the process at high temperatures. Knowledge of these commercial processes is applied toward the development of new graft modification technology, including radical initiated polymer addition to alkynes, and a new variation of precipitation polymerization chemistry. The thermolysis of bicumene at temperatures ranging from 220°C to 270°C was used to initiate C-H bond addition from alkanes to vinylsilanes in a high-temperature analogue of conventional grafting practice. The initiation mechanism is shown to involve direct hydrogen atom abstraction by intermediate cumyl radicals, as well as autooxidation processes involving cumyl radicals and available oxygen. Conventional peroxide initiated graft modifications of polyethylene with vinylsilanes are examined from the standpoint of reaction dynamics and yields. The influence of peroxide loading and monomer concentration on these reaction variables can be described using a simple quasi-steady state kinetic analysis, while the unusual insensitivity of reaction yields to temperature requires further investigation. A new chemical modification of saturated polymers involving free radical addition to mono-substituted alkynes is presented and examined in terms of reaction yield, graft structure, and changes to molecular weight. Model compounds are used to characterize alkyne grafting products, and to probe the relationship between reagent properties, reaction yields, and product structures. The discovery of cross-linked particles in the products of polypropylene graft modifications with triallyltrimesate has led to a variation of precipitation polymerization wherein C-H bond addition to an allyl monomer contributes to molecular weight growth, thereby incorporating a significant amount of saturated hydrocarbon into the solid phase. The relationships between reaction conditions and solid-phase composition and morphology are discussed. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2008-12-18 14:35:52.483

This thesis has presented experimental evidence for the therapeutic use of semantic desensitization in the modification of a snake phobia. An experiment was conducted utilizing 66 introductory psychology and experimental psychology students, who responded in a strongly negative fashion to the word “snake” as it appeared on a semantic differential scale. S’s were randomly assigned to either an experimental group or one of two control groups, where different procedures were used to test the effectiveness of this technique. A significant reduction in the meaning attended to the word “snake” was found after counterconditioning procedures were used for the experimental group. A slight reduction was found in control group I, as was hypothesized and no reduction was found for control group II. It is concluded that counterconditioning utilizing semantic desensitization is an effective and efficient technique in altering meaning attended to a phobic object.

The general purpose of this study was to investigate Strong's interpersonal influence model. Specifically, the research focus was on client perceptions of the counselor and the effect those perceptions had on outcome for clients with a high level of motivation.The subjects for this study were 44 female and 36 male college students enrolled at Texas A&M University. The 80 subjects randomly selected from a subject pool of 116 had a mean age of 21.38 and ranged from freshman to graduate student. Seventy-two were white, none were black, and eight were of other extractions.A one-way pretest-posttest design with two treatment conditions, high and low perceived counselor power, was utilized. The two groups consisted of 45 and 35 subjects, respectively. Student Counseling Service staff and interns served as the counselors for subjects in the two treatment conditions.The instruments used in this study included the Tennessee Self Concept Scale - Counseling Form (TSCS), the Expectations About Counseling Form - motivation scale (EAC), and the Counselor Rating Form (CRF). The TSCS was used as a pretest and posttest measure of self-concept; the EAC as a measure of motivation; and the CRF as a measure of perceived counselor power.An analysis of variance of the posttest means yielded a significant F value at the .01 level. An analysis of variance of the posttest means using all 116 subjects in the subject pool also yielded a significant F value at the .01 level. The high and low perceived counselor power groups consisted of 63 and 53 subjects, respectively, in second analysis of variance. Therefore, the results of this study empirically support Strong's assertion that interpersonal influence is an important factor effecting counseling/therapy outcome.A true step-wise selection multiple regression analysis using all 116 subjects revealed that of all the predictor variables (expertness, attractiveness, trustworthiness, and motivation) trustworthiness was the best predictor of counseling/therapy outcome (self-concept).

The purpose of this study was to investigate the potential effectiveness of assertive training as a mode of intervention for altering college students' perceptions of the locus of control of reinforcement. Effects of sex and sex and treatment interaction on perceptions of internal-external control were also studied.One measure of the control construct as a personality variable is the Rotter I-E scale. This instrument may be used to distribute individuals along a continuum with regard to whether they perceive themselves as possessing or lacking control over what happens to them and the degree to which they accept responsibility for their behavior and life experiences. The end points of this continuum are labeled internal and external control orientations. Internally oriented individuals perceive reinforcements as contingent upon their personal behavior. Both positive and negative life experiences are, therefore, believed to be consequences of one's actions. On the other end of the continuum are individuals who are externally oriented. These individuals perceive reinforcements to be unrelated to their personal behavior and, therefore, beyond personal control and responsibility. Measures of the control construct have been shown to correlate with some consistency with indices of anxiety and adjustment. Internals appeared to have less debilitating anxiety and to be better adjusted according to selected measures of adjustment. In addition, these individuals tended to describe themselves in more positive terms on self-report inventories than did externals.Researchers in the area of assertive training have reported that no relationship between assertive behavior and control orientation has. been found. The intent of this study was to focus upon that aspect of assertive training which stresses the importance of increasing individuals' behavioral repertoires so that they have a choice about how they behave. It was hypothesized that an emphasis upon the element of choice, and the resultant importance of accepting personal responsibility for that choice, would affect alterations in perceptions of locus of control.Sixty-two undergraduate college students enrolled in either of two sections on Human Growth and Development at a Midwest university were the population for the research. The final sample of 62 students completed the Rotter I-E scale and were randomly assigned within their section to either an assertive training or treatment control group. Two treatment and two treatment control groups resulted. The treatment control groups met during the same time period as the respective assertive training group for the purpose of class-related film-discussions. All groups met for six consecutive weeks during the time regularly scheduled for the section. In the seventh week, the Rotter I-E scale was readministered to all subjects.An analysis of covariance, using pretest scores on the Rotter I-E scale as the covariate, was conducted to determine the effects of treatment, sex, and treatment and sex interaction on perception of locus of control as measured by adjusted posttest scores on the I-E scale. Based upon this analysis, the researcher reached the following conclusions:1. Assertive training had no significant effect upon undergraduate college students' perceptions of internal versus external locus of control.2. Sex had no significant effect upon undergraduate college students' perceptions of internal versus external locus of control.3. Interaction of treatment and sex had no significant effect upon undergraduate college students' perceptions of internal versus external locus of control.

The purpose of this study was the investigation of the effects of instructional sets and modeling on oppositional assertion while statistically controlling assertive predispositions by means of a multivariate analysis of covariance. Scores on the Rathus Assertiveness Schedule (RAS) were used as the covariate and ratings of two components of oppositional assertion, compliance content and global assertiveness, were the dependent variables. Additional measures were taken using the whole IRAS scores and the Poland Factor 1 (PF'1) "Oppositional Assertion" scores of the RAS in a repeated measures ANOVA design.All subjects in this study were female undergraduate students of Ball State University. The treatment of the, subjects was as follows: The entire potential subject pool (students taking an introductory general psychology course in the Department of General and Experimental Psychology, Ball State University, Spring Quarter, 1976) was administered the RAS being given no information regarding the purpose of this task. The RAS protocols of the male students were removed while those from the female students were retained. Three weeks later a female confederate recruited female subjects for "an experiment on women." These subjects were then randomly assigned to one of the three treatment conditions, videotaped assertive modeling alone, modeling with behavioral instructions focusing on the known components of assertiveness, or modeling with instructions focusing on the psychoanalytic constructs of ego autonomy. A no modeling control treatment could not be included because of subject and design problems. The effects of pure modeling effects can be inferred by use of the PF 1 of the RAS. Each subject was individually shown the Training Film and immediately afterwards was given a series of ten videotaped test situations to which she was to respond. These responses were recorded on audiotape andgiven to three judges for rating. Subjects were then asked to complete a RAS and a general nonempirical questionnaire, and were then debriefed by the experimenter.Three raters were trained by the experimenter and each heard and evaluated every tape. Three-way interjudge reliability was very high with r = .882 for compliance and r = .798 for global assertion. These ratings were summed and entered in the MANCOVA design.Results of the data analysis revealed surprising outcomes. The RAS did not covary significantly with the dependent behavioral variables. With the possibility of covariate analysis obviated; a MANOVA was performed using the remaining behavioral data. No F2 value exceeded 1.00 indicating no behavioral difference between the treatments. There was also no significant difference between the pre- and post-test scores of the full RAS. Significant results were obtained using PF 1 of the RAS. The treatment incorporating psychoanalytic constructs in the instructions showed the greatest magnitude of increased oppositional assertion (t = 5.38, p_<.001).' The group with behavioral instructions also increased significantly (t = 2.77, P_<-05) while the group receiving modeling alone did not significantly improve (t = 0.06, P_>.05), Additional post hoc analysis indicated that the randomization had failed to control. all variables. The behavioral group was significantly different from the modeling-only group (C = 1.76, p_ .001) at pre-test, with no significant differences in the other comparisons. On post-test both the behavioral and the psychoanalytic groups here significantly (t = 6.96, P <.001; t =7.03, p <.001) different from the modeling only group but not from each other.The conclusions were made that the multivariate approaches had failed to reveal significant changes because of severe (>33%) subject attrition (N after attrition = 39). The significant findings using PF 1 of the RAS were seen as evidence that the treatments had been effective in modifying assertion, with the treatment including psychoanalytic constructs perhaps being more effective. No generalization to other forms of assertiveness was seen.The recommendation was made for additional research on inter-theoretical application of assertion training. The possibility of salutory therapeutic effects resulting from combining behavioral and intra-psychic insight approaches was suggested.