Inferring the sign of social relationships from online interactions is a fundamental challenge in social network analysis. Existing approaches typically rely on sentiment analysis to label individual interactions as positive or negative, then aggregate these labels to assign a sign to the relationship. However, sentiment analysis captures the valence of the content being discussed rather than the nature of the relational exchange itself, a conflation that can lead to systematic misclassification. In this paper, we propose a methodology that addresses this limitation by leveraging Large Language Models (LLMs) in a zero-shot setting to identify interaction-level relational signals (specifically, personal praise and personal attacks directed at the interlocutor) as more direct indicators of positive and negative social ties. We evaluate four models spanning open-weight and proprietary architectures (Qwen2.5:7b, Gemma2:9b, GPT-4o, GPT-5.4-mini) across three prompt designs of increasing complexity, on two human-annotated datasets of approximately 298 and 340 texts respectively. Results show that zero-shot LLMs achieve good classification performance on both tasks without any task-specific training data, establishing a practical baseline for relational annotation. Performance differs across tasks: attack detection is robust to prompt design and model choice, while praise detection is more sensitive to both, reflecting the greater subjectivity of positive relational gestures. These findings lay the groundwork for integrating LLM-based relational annotation into sign prediction pipelines.